WO2011027865A1 - Nouveau composé de 2-aza-adamantane et son procédé de production - Google Patents

Nouveau composé de 2-aza-adamantane et son procédé de production Download PDF

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WO2011027865A1
WO2011027865A1 PCT/JP2010/065160 JP2010065160W WO2011027865A1 WO 2011027865 A1 WO2011027865 A1 WO 2011027865A1 JP 2010065160 W JP2010065160 W JP 2010065160W WO 2011027865 A1 WO2011027865 A1 WO 2011027865A1
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group
optionally substituted
alkyl
cycloalkyl
substituted
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勇樹 遠藤
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日産化学工業株式会社
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    • 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

Definitions

  • the present invention relates to a novel 2-azaadamantane compound used for the oxidation reaction of alcohol.
  • Patent Document 1 shows the oxidation reaction of alcohol with 1-Me-AZADO (1-alkyl-2-azaadamantane-N-oxyl), and Non-Patent Document 1 shows unsubstituted 2-azaadamantane-N-oxyl or 1-alkyl.
  • Each of the alcohol oxidation reactions by -2-azaadamantane-N-oxyl is disclosed.
  • Patent Document 2 discloses oxidation of alcohol using 2-azaadamantane-N-oxyl or 2-azaadamantane-N-oxoammonium salt which is unsubstituted or substituted with an alkyl group, alkoxy group, hydroxy group or fluorine atom. The reaction is disclosed.
  • R 1 is a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, mercapto group, amino group, formyl group, carboxyl group, sulfo group, linear or branched C 1-12 alkyl group, C 3 -12 cycloalkyl group, (C 1-12 alkyl) oxy group, (C 3-12 cycloalkyl) oxy group, (C 1-12 alkyl) thio group, (C 3-12 cycloalkyl) thio group, (C 1-12 alkyl) thio group, (C 1-12 alkyl)
  • R 1 is a hydrogen atom, a C 1-4 alkyl group, a halogen atom or a hydroxyl group
  • R 3 and R 4 are each independently a C 1-4 alkyl group, a C 1-4 haloalkyl group, a benzyl group or a phenyl group.
  • N-acyl-5-hydroxy-2-azaadamantane compound represented by the following formula (4) in the presence of an acid catalyst:
  • R 3 -CN (4) (Wherein R 3 represents the same meaning as described above.)
  • R 1 is a hydrogen atom, a C 1-4 alkyl group, a halogen atom or a hydroxyl group
  • R 3 and R 4 are each independently a C 1-4 alkyl group, a C 1-4 haloalkyl group, a benzyl group or a phenyl group.
  • the 2-azaadamantane compound of the present invention has high performance as an oxidation catalyst. Further, since the Rf value is significantly smaller than the product obtained by oxidizing alcohol, separation from the product is easy.
  • 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.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the present specification, the notation “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 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 consisting of 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 a 3-membered ring to a 6-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 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 can be mentioned as specific examples, and each is selected within the range of the designated number of carbon atoms.
  • C a -C b alkenyl is an unsaturated hydrocarbon having a straight or branched chain of a to b carbon atoms and 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- Specific examples include a pentenyl group, a 2,4-dimethyl-2,6-heptadienyl group, a 3,7-dimethyl-2,6-octadienyl group, and the like, which are selected in the range of each 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 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 in the present specification 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 ring to a 6-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 means a cyclic group 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 one or 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 is a linear or branched chain having 1 to 2 carbon atoms and an unsaturated hydrocarbon having one or more triple bonds in the molecule.
  • a group such as ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 1-methyl-2-butynyl, 1,1- Specific examples include a dimethyl-2-propynyl group, a 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 An unsaturated hydrocarbon group having one or more triple bonds in the molecule.
  • the halogen atoms when substituted by two or more halogen atoms, the 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.
  • the aryl group which may be substituted with R a includes a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, and a p-chloro group.
  • Examples of the benzyl group which may be substituted with Ra include benzyl group, o-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, o-chlorobenzyl group, m-chlorobenzyl group, p-chloro group.
  • Examples include benzyl group, o-fluorobenzyl group, p-fluorobenzyl group, o-methoxybenzyl group, p-methoxybenzyl group, p-nitrobenzyl group and p-cyanobenzyl group.
  • R 1 is preferably, for example, a hydrogen atom, a C 1-4 alkyl group, a halogen atom or a hydroxyl group.
  • R 2 is preferably an amino group or an amino group substituted with R 3 .
  • R 3 is preferably, for example, a C 1-4 alkyl group, a C 1-4 haloalkyl group such as trifluoromethyl or trichloromethyl, a benzyl group or a phenyl group.
  • R 4 is preferably, for example, a C 1-4 alkyl group, a C 1-4 haloalkyl group such as trifluoromethyl or trichloromethyl, a benzyl group or a phenyl group.
  • the 2-azaadamantane compound represented by the formula (1) of the present invention can be used in an oxidation reaction using various alcohols as substrates as catalysts.
  • the alcohol compound to be oxidized is not particularly limited, and various kinds of compounds can be mentioned.
  • Alcohols include, for example, primary and secondary alcohols having the formula A—CH 2 —OH, or A—CH (OH) —B, which can be used in the presence of the catalyst, for example, aqueous sodium hypo It can be converted to the corresponding carbonyl compound using an oxidizing agent such as a chlorite solution.
  • an oxidizing agent such as a chlorite solution.
  • the substituents A and B are not particularly limited as long as they are organic groups that do not adversely influence the reaction.
  • the alkyl group may be substituted, the cycloalkyl group may be substituted, May be an aromatic allotrope or heterocycle.
  • Examples of the alkyl group in the “optionally substituted alkyl group” represented by the substituents A and B include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
  • N-pentyl isopentyl, neopentyl, 1-methylpropyl, n-hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 3,3-dimethylpropyl, etc.
  • 1-6 alkyl and the like can be used.
  • the substituent of the alkyl group includes a lower alkoxy group (eg, C 1-6 alkoxy such as methoxy, ethoxy, propoxy, etc.), a halogen atom (eg, fluorine, chlorine, bromine, iodine, etc.), a lower alkyl group.
  • C 1-6 alkyl such as methyl, ethyl, propyl, etc.
  • lower alkenyl group eg, C 2-6 alkenyl such as vinyl, allyl, etc.
  • lower alkynyl group eg, C 2 such as ethynyl, propargyl, etc.
  • optionally substituted amino group optionally substituted hydroxyl group, optionally substituted sulfonyl group, optionally substituted sulfonylamino group, cyano group, nitro group, nitroso group , optionally substituted amidino group, carboxyl group, lower alkoxycarbonyl group (e.g., methoxycarbonyl, such as ethoxycarbonyl C 1- Alkoxycarbonyl, etc.), an optionally substituted carbamoyl group (e.g., 5 to 6 membered monocyclic aromatic heterocycle (e.g., pyridinyl)
  • Examples of the cycloalkyl group in the “optionally substituted cycloalkyl group” represented by the above substituents A and B include C 3-7 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. Can be used.
  • substituent of the cycloalkyl group the same number of the same substituents as those in the “optionally substituted alkyl group” as the above-described substituent can be used.
  • aromatic allotrope or heterocycle of the “optionally substituted aromatic allotrope or heterocycle” represented by the substituents A and B include, for example, a monocyclic or condensed polycyclic aromatic carbocycle, Alternatively, a monocyclic or condensed polycyclic aromatic heterocycle can be used.
  • a C 6-14 aromatic carbocycle (aryl group) or a 5- to 14-membered aromatic heterocycle (heteroaryl group) can be used, and more preferably a C 6-10 aromatic carbocycle (aryl group) or 5 to a 10-membered aromatic heterocyclic (heteroaryl group), more preferably C 6 aromatic carbocyclic (aryl) or 5 or 6-membered aromatic heterocyclic (heteroaryl group).
  • aromatic homocyclic ring examples include, for example, pentazole; C 6-14 aryl groups such as phenyl, naphthyl, anthryl, azulenyl, phenanthryl, acenaphthylenyl, etc., among which phenyl, 1-naphthyl, 2-naphthyl Etc. are particularly preferred.
  • aromatic heterocycle for example, 1 to 3 (preferably 1 to 2) heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom and the like are used as atoms (ring atoms) constituting a ring system.
  • aromatic heterocyclic ring containing at least one can be used.
  • aromatic heterocycle include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1, 3,4-oxadiazolyl, furazanyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, 5- to 6-membered monocyclic aromatic heterocycles such as pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like, and benzofuranyl, isobenzofurany
  • a 5- to 6-membered monocyclic aromatic heterocycle can be preferably used.
  • the substituent of “optionally substituted aromatic homologue or heterocycle” may be protected by a conventional method of organic chemical synthesis, if necessary, and is not particularly limited as long as it does not affect the reaction. There is no restriction, and it may be one known in the art.
  • Examples of the 2-azaadamantane compound represented by the formula (1) of the present invention include 5-amino-2-azaadamantane-N-oxyl (5-NH 2 -AZADO), 5-acetylamino-2-azaadamantane. -N-oxyl (5-NHAc-AZADO) and the like.
  • the 2-azaadamantane compound represented by the formula (1) of the present invention is used as an alcohol oxidation catalyst, the amount of the 2-azaadamantane compound used is preferably 0.001 mol% to 50 mol% with respect to the substrate alcohol. More preferably, it is 0.1 mol% to 10 mol%.
  • oxygen gas (100% oxygen), air, or a mixed gas of oxygen gas and an inert gas such as nitrogen can be used in the case of oxygen oxidation.
  • hypohalite anions such as hypochlorite and hypobromite can be used.
  • Examples of the counter cation of the hypohalite anion include sodium and calcium.
  • nitrite compounds include, for example, lithium nitrite, sodium nitrite, potassium nitrite, calcium nitrite, barium nitrite, nitrites such as 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.
  • sodium nitrite or tertiary butyl nitrite is preferable.
  • the amount of the nitrite compound to be used is preferably 1 mol% to 100 mol%, more preferably 1 mol% to 50 mol%, based on the substrate alcohol.
  • Nitric acid may be used in place of the nitrous acid compound. In that case, the amount of nitric acid used is in accordance with the amount of nitrite compound.
  • hypohalous acid anion such as hypochlorous acid or hypobromous acid
  • the equivalent is preferably 0.1 to 10 equivalents, more preferably 1 to 2 equivalents, relative to one hydroxy group of the alcohol. It is.
  • Such an oxidation reaction can be carried out under mild conditions, and the reaction temperature is preferably in the range of ⁇ 10 ° C. to 200 ° C., more preferably in the range of 0 ° C. to 100 ° C., further preferably in the range of 10 ° C. to 40 ° C.
  • the range of ° C. particularly preferably room temperature.
  • the reaction pressure is preferably from a reduced pressure state in the range of 0.01 to 10 MPa to a pressurized state, more preferably normal pressure (atmospheric pressure).
  • the reaction time is not necessarily constant depending on the alcohol compound as the substrate to be used and the reaction conditions, but is preferably 1 minute to 100 hours, more 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.
  • water alcohols (for example, methanol, ethanol, propanol, butanol, octanol, etc.), cellosolves (for example, methoxyethanol, ethoxyethanol, etc.), aprotic polar organic solvents (for example, dimethylformamide, dimethylsulfoxide, dimethylacetamide, Tetramethylurea, sulfolane, N-methylpyrrolidone, N, N-dimethylimidazolidinone, etc.), ethers (eg diethyl ether, diisopropyl ether, t-butylmethyl ether, tetrahydrofuran, dioxane etc.), aliphatic hydrocarbons ( For example, pentane, hexane, c-hexane, octane, decan
  • an alcohol having an amino substituent that hardly undergoes an oxidation reaction can also be used as a substrate.
  • concentration of the alcohol compound as a substrate in the solvent is preferably 1 to 99% by mass, more preferably 5 to 50% by mass, except when alcohol is used as the solvent.
  • solvent distillation, extraction, recrystallization, filtration, decantation, column chromatography, etc. The target aldehyde, ketone or carboxylic acid compound can be isolated by ordinary purification operations.
  • 5-NH 2 -AZADO can be produced, for example, by the method represented by the following scheme.
  • 5-NHAc-AZADO can be produced, for example, by the method represented by the following scheme.
  • the starting material 5-hydroxy-N-trifluoroacetyl-2-azaadamantane (5-OH-N-CF 3 CO-AZAD) can be produced, for example, by the method represented by the following scheme. it can.
  • TFAA trifluoroacetic acid
  • NTFA N-COCF 3
  • MeCN means acetonitrile
  • the obtained 1,2-dichloroethane layers were combined and concentrated to obtain a brown liquid (4.30 g).
  • a brown liquid raw material N-trifluoroacetyl-2-azaadamantane (1.08 g) was obtained.
  • Example 1 Synthesis of 5- (2-chloroacetamide) -N-trifluoroacetyl-2-azaadamantane 95% sulfuric acid (1.0 eq) in chloroacetonitrile solution (8 ml) of 5-OH-N-CF 3 CO-AZAD (0.80 g) ) And stirred at 90 ° C. for 2 hours. After cooling, toluene (20 ml), water (10 ml) and saturated aqueous sodium hydrogen carbonate were added until the pH reached 8, followed by liquid separation. Furthermore, the aqueous layer was extracted twice with toluene. The obtained toluene layers were combined and concentrated to obtain a brown liquid (1.26 g).
  • Example 7 Alcohol oxidation L-menthol (1.56 g, 10 mmol), catalyst / 0.1 M toluene solution (0.1 mol%), acetonitrile (15.6 g) and 5% by mass aqueous sodium bicarbonate (7.8 g) were cooled to 5 ° C. Subsequently, 11.1 mass% sodium hypochlorite aqueous solution (1.4 eq) was added dropwise over 1 hour to oxidize to L-menton. 150 minutes after the completion of the dropwise addition, the conversion rate was measured by gas chromatography. When 5-NH 2 -AZADO was used as a catalyst, the conversion was 96.6%, and when 5-NHAc-AZADO was used, the conversion was 100%.
  • Example 8 Column separation characteristics of alcohol oxidation product and catalyst 2-azaadamantane compound Rf value was measured under the following conditions.
  • the Rf (Rate of Flow) value is a value obtained by dividing the moving distance of the spot by the moving distance of the solvent in thin layer chromatography (TLC).
  • AZADO represents 2-azaadamantane-N-oxyl
  • HO-AZADO represents 5-hydroxy-2-azaadamantane-N-oxyl
  • NHAc-AZADO represents 5-acetylamino-2-azaadamantane- N-oxyl represents NH 2 -AZADO and 5-amino-2-azaadamantane-N-oxyl.
  • oxidation of various alcohols is performed almost selectively under mild conditions without the need for heating or toxic heavy metal compounds to produce aldehyde compounds, ketone compounds and / or carboxylic acid compounds.
  • the Rf value is significantly smaller than the product obtained by oxidizing alcohol, and separation from the product is easy, so that it is extremely useful industrially.

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  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
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Abstract

L'invention porte sur un nouveau composé qui est utile comme catalyseur d'oxydation pour des composés alcooliques. L'invention porte sur un composé de 2-aza-adamantane représenté par la formule (1) et sur son procédé de production. (Dans la formule (1), N-A représente N-H, N-C(=O)R4, N-O·, N-OH ou N+(=O)X-; X- représente F-, Cl-, Br- ou similaire; R1 représente un atome d'hydrogène, un atome d'halogène ou similaire; R2 représente NH2 ou NHCOR3; et R3 et R4 représentent chacun indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle en C1-6 ou un groupe phényle.)
PCT/JP2010/065160 2009-09-04 2010-09-03 Nouveau composé de 2-aza-adamantane et son procédé de production WO2011027865A1 (fr)

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EP3116052A1 (fr) * 2015-07-08 2017-01-11 Basf Se Cellules métal-oxygène rechargeables

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2012008228A1 (fr) * 2010-07-16 2012-01-19 第一三共株式会社 Procédé d'oxydation d'alcools
JPWO2012008228A1 (ja) * 2010-07-16 2013-09-05 第一三共株式会社 アルコール類の酸化方法
US8871981B2 (en) 2010-07-16 2014-10-28 Tohoku University Method for oxidizing alcohols
JP5763638B2 (ja) * 2010-07-16 2015-08-12 第一三共株式会社 アルコール類の酸化方法
EP3116052A1 (fr) * 2015-07-08 2017-01-11 Basf Se Cellules métal-oxygène rechargeables

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