WO2009145323A1 - Procédé d'oxydation d'un alcool à l'aide d'un composé polycyclique - Google Patents

Procédé d'oxydation d'un alcool à l'aide d'un composé polycyclique Download PDF

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WO2009145323A1
WO2009145323A1 PCT/JP2009/059909 JP2009059909W WO2009145323A1 WO 2009145323 A1 WO2009145323 A1 WO 2009145323A1 JP 2009059909 W JP2009059909 W JP 2009059909W WO 2009145323 A1 WO2009145323 A1 WO 2009145323A1
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group
optionally substituted
alkyl
compound
azaadamantane
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PCT/JP2009/059909
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Japanese (ja)
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好治 岩渕
正俊 澁谷
正樹 富澤
祐二 長田
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日産化学工業株式会社
国立大学法人東北大学
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Priority claimed from JP2008143200A external-priority patent/JP2011153076A/ja
Priority claimed from JP2008228721A external-priority patent/JP2011153077A/ja
Application filed by 日産化学工業株式会社, 国立大学法人東北大学 filed Critical 日産化学工業株式会社
Publication of WO2009145323A1 publication Critical patent/WO2009145323A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/516—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of nitrogen-containing compounds to >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D451/00—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof
    • C07D451/14—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof containing 9-azabicyclo [3.3.1] nonane ring systems, e.g. granatane, 2-aza-adamantane; Cyclic acetals thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D453/00—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids
    • C07D453/02—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/08—Bridged systems
    • 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
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/20—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the present invention relates to a method for oxidizing alcohol with oxygen using a polycyclic compound.
  • Oxidation reaction by air is expected as an ideal oxidation process from the viewpoint of safety and environmental harmony.
  • Examples of the method for oxidizing alcohols using air as an oxidizing agent include examples using palladium compounds (for example, see Non-Patent Document 1 and Non-Patent Document 4), examples using cobalt complexes (for example, see Non-Patent Document 2), ruthenium.
  • Examples using compounds for example, see Non-Patent Document 6
  • examples using 2,2,6,6-tetramethylpyridine-N-oxyl (TEMPO) and its derivatives for example, Patent Document 1 and Non-Patent Document 3) 5, 7, 8, 9, 10, 11) are known.
  • TEMPO 2,2,6,6-tetramethylpyridine-N-oxyl
  • TEMPO 2,2,6,6-tetramethylpyridine-N-oxyl
  • TEMPO 2,2,6,6-tetramethylpyridine-N-oxyl
  • TEMPO 2,2,6,6-tetramethylpyridine-N-oxyl
  • An object of the present invention is to provide a method for oxidizing alcohol with oxygen, which does not require a toxic heavy metal compound or the like in any alcohol oxidation, and is highly economical and safe for the environment.
  • the present inventors have found an oxidation method using a polycyclic compound as a catalyst and oxygen as an oxidizing agent, thereby completing the present invention.
  • R 1 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, a mercapto group, an amino group, a formyl group, a carboxyl group, a sulfo group, a C 1-12 alkyl group, a C 3-12 cyclo group.
  • R 4 and R 5 each independently represent the same meaning as R 1 , or R 4 and R 5 may be taken together to form a methylene which may be substituted with R 1
  • R a is halogen, C 1-6 alkyl group, C 1-6 haloalkyl group, C 3-6 cycloalkyl group, C 1-6 alkoxy group, C 1-6 alkoxy C 1-6 alkyl group, C 1- 6 alkylsulfenyl C 1-6 alkyl group, C 1-6 haloalkoxy group, C 1-6 alkylsulfenyl group, C 1-6 alkylsulfinyl group, C 1-6 alkylsulfonyl group, C 1-6 haloalkylsulfenyl Phenyl group, C 1-6 haloalkylsulfinyl group, C 1-6 haloalkylsulfonyl group, C 2-6 alkenyl group, C 2-6 haloalkenyl group, C 2
  • R 3 may be the same or different from each other, and represents a hydrogen atom, a fluorine atom, a hydroxy group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, provided that R 3 Any one or more of them is a fluorine atom or a hydroxy group
  • NO represents NO.
  • Represents N-OH, or represents N + ( O)
  • X ⁇ represents F ⁇ , Cl -, Br -, I -, ClO 2 -, ClO 4 -, IO 4 -, NO 2 -, NO 3 -, SO 4 2-, BF 4 -, PF 6 -, SbCl 5 -, SbF 6 -, XeF 2 -, (CF 3 SO 2 ) 2 N - Table in representing a) -, CH 3 CO 2 - , CF 3 CO 2 -, 4-CH 3 C 6 H 4 SO 2 O - or
  • alcohols such as primary alcohols and secondary alcohols are oxidized with an oxygen-containing gas such as oxygen gas or air under mild conditions without the need for heating or toxic heavy metal oxides.
  • oxygen-containing gas such as oxygen gas or air
  • the compound, ketone compound and / or carboxylic acid compound can be produced almost selectively in high yield.
  • the polycyclic compound used in the present invention is represented by the above formula (1).
  • the notation method of each group in Formula (1) is as follows.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the expression “halo” also represents these halogen atoms.
  • C a -C b alkyl represents a linear or branched hydrocarbon group having a carbon number of a to b, such as methyl group, ethyl group, n-propyl group, i-propyl group.
  • n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1, 1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1,1-dimethylbutyl group, 1,3
  • Specific examples include -dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like, and each is selected within the range of the designated number of carbon atoms.
  • C a -C b haloalkyl refers to a linear or branched hydrocarbon group comprising a to b carbon atoms, in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom.
  • the halogen atoms when substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other.
  • fluoromethyl group chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, chlorofluoromethyl group, dichloromethyl group, bromofluoromethyl group, trifluoromethyl group, chlorodifluoromethyl group, dichlorofluoromethyl group, trichloromethyl Group, bromodifluoromethyl group, bromochlorofluoromethyl group, dibromofluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2-chloro-2-fluoroethyl Group, 2,2-dichloroethyl group, 2-bromo-2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2-dichloro-2 -Fl group, 2-chloro-2,2-
  • C a -C b cycloalkyl represents a cyclic hydrocarbon group having a to b carbon atoms, and forms a monocyclic or complex ring structure having 3 to 6 members. I can do it. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms.
  • cyclopropyl group 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group, 2- Specific examples include methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, bicyclo [2.2.1] heptan-2-yl group, etc. , Each selected range of carbon atoms.
  • C a -C b halocycloalkyl represents a cyclic hydrocarbon group having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom.
  • a monocyclic or complex ring structure from 3 to 6 membered rings can be formed.
  • Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the substitution with a halogen atom may be a ring structure part, a side chain part, They may be both, and when substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other.
  • 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, 2,2-dichloro-1-methyl Cyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group , 4- (trifluoromethyl) cyclohexyl group and the like are listed as specific examples, and each is selected within the range of the designated number of carbon atoms.
  • C a -C b alkenyl is a linear or branched chain having a carbon number of a to b, and an unsaturated carbon having one or more double bonds in the molecule.
  • vinyl group 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 2-pentenyl group, 2- Methyl-2-butenyl group, 3-methyl-2-butenyl group, 2-ethyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 2-hexenyl group, 2-methyl-2-pentenyl group, Specific examples include 2,4-dimethyl-2,6-heptadienyl group, 3,7-dimethyl-2,6-octadienyl group and the like, and each is selected within the range of the designated number of carbon atoms
  • C a -C b haloalkenyl is a straight chain or branched chain consisting of a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and Represents an unsaturated hydrocarbon group having one or more double bonds in the molecule.
  • the halogen atoms may be the same as or different from each other.
  • C a -C b cycloalkenyl represents a cyclic unsaturated hydrocarbon group having 1 to 2 carbon atoms and having 1 to 2 carbon atoms.
  • a monocyclic or complex ring structure from a member ring to a six-membered ring can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-.
  • 2-cyclopenten-1-yl group, 3-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, bicyclo [2.2.1] -5-hepten-2- Specific examples include yl groups and the like, and each is selected within the range of the designated number of carbon atoms.
  • C a -C b halocycloalkenyl refers to a cyclic one having 1 to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom.
  • it represents an unsaturated hydrocarbon group having two or more double bonds, and can form a monocyclic or complex ring structure having 3 to 6 members.
  • Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-.
  • substitution by a halogen atom may be a ring structure part, a side chain part or both of them, and when substituted by two or more halogen atoms, those halogen atoms May be the same as or different from each other.
  • a 2-chlorobicyclo [2.2.1] -5-hepten-2-yl group and the like are given as specific examples, and each group is selected within the range of the designated number of carbon atoms.
  • C a -C b alkynyl represents a linear or branched chain consisting of a to b carbon atoms and an unsaturated carbonization having one or more triple bonds in the molecule.
  • ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 1-methyl-2-propynyl group, 2-pentynyl group, 1-methyl-2-butynyl group, 1,1-dimethyl-2 Specific examples include -propynyl group, 2-hexynyl group and the like, and each is selected within the range of the designated number of carbon atoms.
  • C a -C b haloalkynyl as used herein is a straight or branched chain consisting of a to b carbon atoms, wherein a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and Represents an unsaturated hydrocarbon group having one or more triple bonds in the molecule.
  • these halogen atoms may be the same as or different from each other.
  • Specific examples include 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like. Each of which is selected for each specified number of carbon atoms.
  • phenyl group o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl Group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl group, p-cyanophenyl group, ⁇ -naphthyl group, ⁇ -naphthyl group, o- Biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9- Phenanthryl
  • benzyl group optionally substituted by R a , benzyl group, o-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, o-chlorobenzyl group, m-chlorobenzyl group, p-chlorobenzyl Group, o-fluorobenzyl group, p-fluorobenzyl group, o-methoxybenzyl group, p-methoxybenzyl group, p-nitrobenzyl group, p-cyanobenzyl group.
  • the alcohol compound to be oxidized is not particularly limited, and includes various alcohol compounds. Among these alcohol compounds, menthol, 4-methoxybenzyl alcohol and the like are preferable.
  • Examples of the polycyclic compound represented by (1) used in the present invention include 2-azaadamantane-N-oxyl (AZADO), 1-methyl-2-azaadamantane-N-oxyl (1-Me-AZADO). And 2-azaadamantane-N-oxyl compounds in which a hydroxy group or a fluorine atom is independently substituted at the 5-position and / or the 7-position.
  • AZADO 2-azaadamantane-N-oxyl
  • 1-methyl-2-azaadamantane-N-oxyl 1-methyl-2-azaadamantane-N-oxyl
  • 2-azaadamantane-N-oxyl compounds in which a hydroxy group or a fluorine atom is independently substituted at the 5-position and / or the 7-position.
  • AZADO 1-fluoro-2-azaadamantane-N-oxyl (1-F-AZADO), 5-fluoro-2-azaadamantane-N-oxyl (5-F-AZADO), 5-fluoro-1 -Methyl-2-azaadamantane-N-oxyl (5-F-1-Me-AZADO), 5,7-difluoro-1-methyl-2-azaadamantane-N-oxyl (5,7-F 2 -1 -Me-AZADO), 1-methyl-2-azaadamantane-N-oxyl (1-Me-AZADO), 1-methyl-5-hydroxy-2-azaadamantane-N-oxyl (1-Me-5-OH) -AZADO), 5-methoxy-1-methyl-2-azaadamantane-N-oxyl (5-MeO-1-Me-AZADO), 5-hydroxy-2-azaadamantane-N-oxyl (5-OH-AZADO) ), 9-azabic
  • N-hydroxy compounds include N-hydroxy-1-fluoro-2-azaadamantane (1-F-AZADOH), N-hydroxy-5-fluoro-2 -Azaadamantane (5-F-AZADOH), N-hydroxy-5-fluoro-1-methyl-2-azaadamantane (5-F-1-Me-AZADOH), N-hydroxy-5,7-difluoro-1 -Methyl-2-azaadamantane (5,7-F 2 -1-Me-AZADOH), N-hydroxy-1-methyl-2-azaadamantane (1-Me-AZADOH), N-hydroxy-1-methyl- 5-hydroxy-2-azaadamantane (1-Me-5-OH-AZADOH), N-hydroxy-5-methoxy-1-methyl-2-azaadamantane (5-MeO-1-Me-AZADOH), N- Hydroxy-5-hydroxy-2-azaadamantane (5-OH-AZADOH), N-N-hydroxy-1-fluoro-2-azaadamantan
  • Polycyclic compounds in which NO represents N + ( ⁇ O) X ⁇ that is, oxoammonium salts include, for example, 2-azaadamantane-N-oxoammonium salt (AZADO + X ⁇ ), 1-methyl-2-azaadamantane -N- oxo ammonium salts (1-Me-AZADO + X -), 5 -position and / or 7-position hydroxy group or a fluorine atom each independently are substituted 2-aza-adamantan -N- oxo ammonium salts Among them, for example, AZADO + X ⁇ , 1-fluoro-2-azaadamantane-N-oxoammonium salt (1-F-AZADO + X ⁇ ), 5-fluoro-2-azaadamantane-N-oxoammonium salt (5-F-AZADO + X -), 5- fluoro-1-methyl-2-aza-adamantan -N
  • X - as the F -, Cl -, Br - , I -, ClO 2 -, ClO 4 -, IO 4 -, NO 2 -, NO 3 -, SO 4 2-, BF 4 -, PF 6 -, SbCl 5 -, SbF 6 -, XeF 2 -, (CF 3 SO 2) 2 N -, CH 3 CO 2 -, CF 3 CO 2 -, 4-CH 3 C 6 H 4 SO 2 O -, CF 3 SO 2 O 2- and the like can be mentioned, and Cl-or NO 3- is preferred.
  • the amount of the polycyclic compound used is preferably 0.01 mol% to 50 mol%, more preferably 0.1 mol% to 10 mol%, based on the substrate alcohol.
  • nitrite compound of the present invention examples include nitrites such as lithium nitrite, sodium nitrite, potassium nitrite, calcium nitrite, barium nitrite, silver nitrite; ethyl nitrite, isoamyl nitrite, isobutyl nitrite, Nitrite esters such as tertiary butyl nitrate, normal butyl nitrite, isopropyl nitrite, normal propyl nitrite, and adamantyl nitrite. Of these, sodium nitrite and tertiary butyl nitrite are preferable.
  • the amount of the nitrite compound to be used is 1 mol% to 100 mol%, preferably, for example, 1 mol% to 50 mol% with respect to the substrate alcohol.
  • Nitric acid may be used in place of the nitrous acid compound.
  • the amount of nitric acid used is in accordance with the amount of nitrite compound.
  • the oxidation reaction of the present invention is characterized in that it can be carried out under mild conditions, and the reaction temperature can also be carried out at room temperature. Furthermore, it can be carried out in the range of ⁇ 10 ° C. to 200 ° C.
  • As the reaction pressure normal pressure (atmospheric pressure) is sufficient, but the reaction can be carried out in a reduced pressure state or a pressurized state in the range of 0.01 to 10 MPa (gauge pressure) as necessary.
  • the oxidation reaction is preferably performed at room temperature and normal pressure.
  • the reaction time is not necessarily constant depending on the alcohol compound as a substrate to be used and the reaction conditions, but is usually 1 minute to 100 hours, preferably 5 minutes to 24 hours.
  • a solvent can be used as necessary.
  • the solvent is not limited as long as it does not inhibit the progress of the reaction, and is water, alcohols (for example, methanol, ethanol, propanol, butanol, octanol, etc.), cellosolves (for example, methoxyethanol, ethoxyethanol, etc.), aprotic Polar organic solvents (eg, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, tetramethylurea, sulfolane, N-methylpyrrolidone, N, N-dimethylimidazolidinone, etc.), ethers (eg, diethyl ether, diisopropyl ether, t- Butyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (eg pentane, hexane, c-hexane, oc
  • an alcohol having an amino substituent which does not easily undergo an oxidation reaction, can be used as a substrate.
  • concentration of the alcohol compound as a substrate in the solvent is preferably 1 to 99% by mass, and more preferably 5 to 50% by mass except when alcohol is used as the solvent.
  • oxygen gas 100% oxygen
  • air can be used as oxygen as an oxidizing agent.
  • 1-Me-AZADO can be produced by the method described in International Patent Application Publication WO2006 / 001387A1 pamphlet.
  • 5-F-1-Me-AZADO can be produced by the method represented by the following scheme.
  • 1-Methyl-N-benzyloxycarbonyl-2-azaadamantane 6 can be produced according to International Patent Application Publication WO2006 / 001387A1 pamphlet.
  • 5,7-F 2 -1-Me-AZADO can be produced by the method represented by the following scheme.
  • 5-MeO-1-Me-AZADO can be produced by the method represented by the following scheme.
  • 5-F-AZADO can be produced by the method represented by the following scheme.
  • the carboxylic acid compound represented by the formula (19) can be produced by a method according to, for example, J. Org. Chem., Vol. 39, No. 26, p3822 (1974).
  • 1-F-AZADO can be produced by a method represented by the following scheme.
  • 1-hydroxy-N-benzyloxycarbonyl-2-azaadamantane 31 can be produced according to the description in J. Am. Chem. Soc., 2006, 128, p8412-8413.
  • Non-commercial nitrous acid compounds can be produced according to Synthesis, 2004, 11, 1747-1749.
  • the oxoammonium nitrate of the present invention comprises N 2 -oxyl compound represented by the following formula (2) or N-hydroxy compound represented by the following formula (3) obtained as described above, and NO 2 (nitrogen dioxide). ), N 2 O 4 (dinitrogen tetroxide) or a nitrous acid compound.
  • Examples of the method for producing oxoammonium nitrate of the present invention include a method in which an N-oxyl compound represented by the formula (2) is reacted with NO 2 or N 2 O 4 gas in a solvent.
  • it can be carried out by a method in which NO 2 gas is blown into a diethyl ether solution of the N-oxyl compound represented by the formula (2) and reacted at room temperature.
  • the oxoammonium nitrate of the present invention can be obtained by reacting the compound represented by the formula (2) under the same conditions as in the above-mentioned alcohol oxidation in the absence of the substrate alcohol.
  • Example 1 Production of catalyst Production of 1-methyl-N-trifluoroacetyl-2-azaadamantane (7) 1-methyl-N-benzyloxycarbonyl-2-aza produced according to International Patent Application Publication WO2006 / 001387A1 Pamphlet Pd / C (189 mg) containing 5% by mass of Pd was added to a solution of adamantane 6 (1.89 g, 6.61 mmol) in MeOH (0.1 M, 66 mL), and the mixture was stirred for 2 hours under H 2 stream. The reaction solution was filtered through Celite (registered trademark manufactured by Celite Corporation), and the solvent was removed under reduced pressure.
  • Celite registered trademark manufactured by Celite Corporation
  • Tetrahydropyran (88.5 mL) and benzyl alcohol 91.6 mL (885 mmol) were added to the reaction solution, and heated and refluxed until the disappearance of endo-bicyclo [3.3.1] non-6-ene-3-carbonylazide was confirmed. did. After allowing to cool, water and ethyl acetate were added for liquid separation, and the organic layer was washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and concentrated.
  • N-trifluoroacetyl-2-azaadamantane 22 500 mg, 2.14 mmol
  • CCl 4 -MeCN-H 2 O 1.65 M; 1.3 mL-1.1 M; 1.9 mL-1.1 M; 1.9 mL
  • NaIO 4 1.05 g, 4.90 mmol
  • RuCl 3 44 mg, 0.214 mmol
  • 5-fluoro-N-trifluoroacetyl-2-azaadamantane (25) 5-hydroxy-N-trifluoroacetyl-2-azaadamantane 23 (549 mg, 2.20 mmol) of CH 2 Cl 2 (1.43 M, 1.5 mL) DAST (0.58 mL, 4.40 mmol) was added to the solution at ⁇ 78 ° C., the temperature was gradually raised, and the mixture was stirred at 0 ° C. for 1 hour. Then, after diluting with Et 2 O, H 2 O was added and extracted with AcOEt, and the organic layer was washed with H 2 O and dried over MgSO 4 .
  • N-benzyloxycarbonyl-1-fluoro-2-azaadamantane (32) 1-hydroxy-N-benzyloxycarbonyl-2-azaadamantane 31 (227 mg, 0.79 mmol) in CH 2 Cl 2 (1.43 M, 0.55 mL) DAST (0.32 mL, 2.37 mmol) was added to the solution at ⁇ 78 ° C., the temperature was gradually raised, and the mixture was stirred at 0 ° C. for 1 hour. Then, after diluting with Et 2 O, H 2 O was added and extracted with AcOEt. The organic layer was washed with H 2 O and dried over MgSO 4 , and the solvent was distilled off under reduced pressure.
  • Example 2 Oxygen Oxidation Using N-Oxyl Compound Sodium nitrite (5 mol% of alcohol compound) or tartar nitrite was added to acetic acid solution (0.33 mol / L) or methylene chloride solution (0.33 mol / L) of alcohol compound. Addition of Libutyl (30 mol% of alcohol compound) and 5-fluoro-2-azaadamantane-N-oxyl (5 mol% of alcohol compound) and confirmation of the disappearance of the raw material alcohol with oxygen balloon attached at room temperature Stir vigorously until After completion of the reaction, water and methylene chloride were added for liquid separation, and the organic layer was washed with water to obtain the desired ketone or aldehyde.
  • t-Bu tertiary butyl group
  • AZADO 2-azaadamantane-N-oxyl
  • 1-F-AZADO 1-fluoro-2-azaadamantane-N-oxyl
  • 5-F-AZADO 5-Fluoro-2-azaadamantane-N-oxyl
  • 1-Me-AZADO 1-methyl-2-azaadamantane-N-oxyl
  • 1-Me-5-F-AZADO 1-methyl-5-fluoro- 2-Azaadamantane-N-oxyl
  • 5,7-F 2 -1-Me-AZADO 5,7-difluoro-1-methyl-2-azaadamantane-N-oxyl
  • 1-Me-5-OH-AZADO 1-methyl-5-hydroxy-2-azaadamantane-N-oxyl
  • 5-MeO-1-Me-AZADO 5-methoxy-1-methyl-2-azaadamantane-N-oxyl
  • 5-OH-AZADO 5-meth
  • Entry is the example number
  • substrate is the substrate
  • product is the product
  • cat is the catalyst
  • Time (h) is the reaction time (unit: time)
  • Yield is the yield
  • recover represents raw material recovery
  • methyl ester represents methyl ester
  • carboxylic acid represents carboxylic acid
  • trace represents trace amount
  • balloon represents balloon
  • rt represents room temperature
  • ref represents reference.
  • NaNO 2 in the reaction formula is sodium nitrite
  • FeCl 3 ⁇ 6H 2 O is ferric chloride ⁇ hexahydrate
  • AcOH is acetic acid
  • t-BuONO is tertiary butyl nitrite
  • CH 2 N 2 represents diazomethane.
  • NR indicates that the reaction did not proceed
  • ⁇ indicates that the reaction was not measured
  • GC yield indicates the measurement result of the yield by the gas chromatography fluff method. .
  • Example 3 Reaction example 3 in which the solvent for the oxidation reaction was changed 3-1 MeCN / AcOH solvent
  • 2-octanol (3.91 g), 2-azaadamantane-N-oxyl (0.0229 g), acetonitrile (7.8 g ), Acetic acid (3.6 g) and NaNO 2 (0.831 g) in this order, and the inside of the reaction vessel was purged with oxygen, and then in an oxygen atmosphere (0.1 MPa) (gauge pressure, the same applies hereinafter) at room temperature. Stir for 4 hours.
  • the yield of the desired 2-octanone was 98% (GC yield (measurement of yield by gas chromatography method, the same applies hereinafter)).
  • Example 4 Reaction in a system using an N-hydroxy-2-azaadamantane compound
  • 2-octanol (1.30 g), N-hydroxy-2-azaadamantane (0.0154 g), acetic acid (3.9 g) and NaNO 2 (0.415 g) was sequentially added, and the inside of the reaction vessel was purged with oxygen, and then stirred at room temperature for 15 hours in an oxygen atmosphere (0.1 MPa).
  • the target yield of 2-octanone was 89% (GC yield).
  • Example 5 Reaction in a system using nitric acid
  • 2-octanol 0.392 g
  • 2-azaadamantane-N-oxyl AZADO
  • acetic acid 1.2 g
  • 65% by mass nitric acid An aqueous solution (0.0288 g) was sequentially added, and the reaction vessel was purged with oxygen, and then stirred at room temperature in an oxygen atmosphere (0.1 MPa) for 7 hours.
  • the yield of the desired 2-octanone was 99%.
  • Example 6 Preparation Example of Oxoammonium Halide Salt
  • Example 6-1 Preparation of Chloride Salt Chlorine at room temperature in a solution of 1-Me-AZADO (1920 mg, 11.55 mmol) in CCl 4 (23.1 mL, 0.5 M) Gas was blown in and stirred vigorously. The precipitated crystals were collected by filtration with a glass filter, washed with cooled Et 2 O, and dried under reduced pressure to obtain 1-Me-AZADO + Cl ⁇ (2316 mg, 99%).
  • Example 6-2 Using the preparation bromine bromide, in the same manner as in Example 6-1, 1-Me-AZADO + Br - ( actual counter ions Br 3 -) was obtained.
  • Example 7 Preparation of oxoammonium nitrate NO 2 gas generated by adding copper powder to concentrated HNO 3 to Et 2 O solution (red) of 5-F-AZADO (16 mg, 0.094 mmol) in a water bath Infused. After confirming that the color of the solution became transparent, the precipitated solid was filtered. Thereafter, the precipitated yellow solid was thoroughly washed with Et 2 O. The obtained solid was dried under reduced pressure with a vacuum pump to obtain 5-F-AZADO + NO 3 ⁇ (20.5 mg, 0.088 mmol, 94%) as a yellow solid.
  • Example 9 Oxygen oxidation using oxoammonium nitrate
  • Oxoammonium nitrate of 5-fluoro-2-azaadamantane (5 mol% of the alcohol compound) was added to an acetic acid or methylene chloride solution of the alcohol compound, and the starting alcohol compound at room temperature. The mixture was stirred vigorously until disappearance was confirmed. After completion of the reaction, water and methylene chloride were added for liquid separation, and the organic layer was washed with water to obtain the desired ketone or aldehyde.
  • 2-octanol (1.30 g), 2-azaadamantane-N-oxoammonium nitrate (0.0214 g), acetic acid (3.91 g) and NaNO 2 (0.413 g) were added to the reaction vessel in the order shown on the left.
  • the inside of the reaction vessel was purged with oxygen, and then stirred at room temperature in an oxygen atmosphere (0.1 MPa) for 15 hours.
  • the target yield of 2-octanone was 92% (GC yield).
  • Air is air
  • TBS is tertiary butyldimethylsilyl group
  • Cbz is benzyloxycarbonyl group
  • Bz is benzoyl group
  • Ac is acetyl group
  • Me is methyl group
  • Ph is phenyl group
  • THP is tetrahydro Pyran
  • HFIP represents 1,1,1,3,3,3-hexafluoro-2-propanol
  • DMSO represents dimethyl sulfoxide.
  • 5-F-AZADO + NO 3 - represents an oxo ammonium nitrate 5-fluoro-2-aza-adamantane.
  • the present invention oxidizes various alcohols with oxygen in the air, almost selectively under mild conditions without the need for heating or toxic heavy metal compounds, and provides aldehyde compounds, ketone compounds and / or carboxylic acids.
  • the compound can be produced and is extremely useful industrially.

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Abstract

L'invention porte sur un nouveau procédé d'oxydation d'un composé alcool. Le procédé d'oxydation d'un composé alcool, qui est exprimé par le schéma (1), est caractérisé par l'utilisation d'oxygène en présence d'un composé polycyclique et un composé acide nitreux.
PCT/JP2009/059909 2008-05-30 2009-05-29 Procédé d'oxydation d'un alcool à l'aide d'un composé polycyclique WO2009145323A1 (fr)

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JP2008143200A JP2011153076A (ja) 2008-05-30 2008-05-30 多環式ｎ−オキシル化合物を用いるアルコールの酸化方法
JP2008-228721 2008-09-05
JP2008228721A JP2011153077A (ja) 2008-09-05 2008-09-05 オキソアンモニウム硝酸塩を用いるアルコールの酸化方法

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EP2221306A1 (fr) * 2007-11-20 2010-08-25 Nissan Chemical Industries, Ltd. Procédé de production de 2-azaadamantane
WO2011027865A1 (fr) * 2009-09-04 2011-03-10 日産化学工業株式会社 Nouveau composé de 2-aza-adamantane et son procédé de production
JP2011153104A (ja) * 2010-01-28 2011-08-11 Nisshinbo Holdings Inc アルコールの酸化方法
WO2012004069A1 (fr) * 2010-07-06 2012-01-12 Evonik Degussa Gmbh Procédé de préparation de 2,5-diformylfurane et de ses dérivés
WO2012008228A1 (fr) * 2010-07-16 2012-01-19 第一三共株式会社 Procédé d'oxydation d'alcools
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JP2015166325A (ja) * 2014-03-04 2015-09-24 国立大学法人東北大学 アルコキシアミン化合物、アルコキシアミン型アルコール酸化触媒及びそれを用いたアルコール酸化方法
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