Production of optically active ketone
AssigneeToray Industries, Inc.
InventorsHaruyo Sato, Sakie Nakai, Keiko Funabashi, Shiho Iwata
Life of this patent
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Abstract
Process for producing an optically active ester by reaction of a racemic alcohol with an optically active amino or tartaric acid derivative, a process for producing an optically active alcohol by hydrolysis of the optically active ester, a process for converting an alcohol into a ketone by oxidation, a method for stably storing an optically active ketone, and a new optically active amino acid ester and a new optically active tartaric acid ester.
Claims54
A process for producing an optically active amino acid ester, said process comprising reacting a racemic alcohol with an optically active amino acid to produce an amino acid ester, and performing diastereomer resolution thereon, wherein said optically active amino acid is at least one acid selected from the group consisting of an optically active α-amino acid and an N-substituted amino acid and wherein said diastereomer resolution is performed by a process selected from the group consisting of crystallization separation, column separation, and simulated moving bed separation.
A process for preparing a tartaric acid ester, comprising reacting a racemic secondary alcohol with an optically active tartaric acid derivative anhydride represented by the formula (IX) below,
- where R8 and R9 are identical or different, each being selected from the group consisting of a C1-4 alkyl group, alkoxyl group, phenyl group, C1-4 alkylcarbonyl group, unsubstituted arylcarbonyl group, and an arylcarbonyl group substituted with a C1-4 alkyl group or halogen atom;
- and wherein the tartaric acid skeleton is of (R,R) conformation or (S,S) conformation, said racemic secondary alcohol being represented by the formula (X) below
- where R10 and R11 are different, each being selected from the group consisting of an unsubstituted or substituted C1-4 alkyl group, an unsubstituted or substituted phenyl group, with the substituent being a C1-4 alkyl group, or a halogen atom, and an aralkyl group;
- and wherein R10 and R11 may combine to form an alicyclic alkyl group substituted by a C1-4 alkyl group or an alkoxyl group, thereby producing a tartaric acid ester represented by the formula (XI) below,
- where R8, R9, R10, and R11 are defined as above,
- further characterized in that said reaction is carried out in the presence of a Lewis acid.
A process for producing a tartaric acid ester, comprising reacting a racemic secondary alcohol with an optically active tartaric acid derivative anhydride represented by the formula (IX),
- where R8 and R9 are identical or different, each being selected from the group consisting of a C1-4 alkyl group, alkoxyl group, phenyl group, C1-4 alkylcarbonyl group, unsubstituted arylcarbonyl group, and an arylcarbonyl group substituted with a C1-4 alkyl group or halogen atom;
- and wherein the tartaric acid skeleton is on (R,R) conformation or (S,S) conformation, said racemic secondary alcohol being represented by the formula (X)
- where R10 and R11 are different, each being selected from the group consisting of an unsubstituted or substituted C1-4 alkyl group, an unsubstituted or substituted phenyl group, with the substituent being a C1-4 alkyl group, or a halogen atom, and an aralkyl group;
- and wherein R10 and R11 may combine to form an alicyclic alkyl group substituted by a C1-4 alkyl group or an alkoxyl group,
- thereby producing a tartaric acid ester represented by the formula (XI),
- where R8, R9, R10 and R11 are defined as above, wherein said racemic secondary alcohol is 2-methoxycyclohexanol, further characterized in that said reaction is carried out in the presence of a Lewis acid.
A process for producing a tartaric acid ester comprising reacting a racemic secondary alcohol with an optically active tartaric acid derivative anhydride represented by the formula (IX),
- where R8 and R9 are identical or different, each being selected from the group consisting of a C1-4 alkyl group, alkoxyl group, phenyl group, C1-4 alkylcarbonyl group, unsubstituted arylcarbonyl group, and an arylcarbonyl group substituted with a C1-4 alkyl group or halogen atom;
- and wherein the tartaric acid skeleton is of (R,R) conformation or (S,S) conformation, said racemic secondary alcohol being represented by the formula (X)
- where R10 and R11 are different, each being selected from the group consisting of an unsubstituted or substituted C1-4 alkyl group, an unsubstituted or substituted phenyl group, with the substituent being a C1-4 alkyl group, or a halogen atom, and an aralkyl group;
- and wherein R10 and R11 may combine to form an alicyclic alkyl group substituted by a C1-4 alkyl group or an alkoxyl group, thereby producing a tartaric acid ester represented by the formula (XI),
- where R8, R9, R10 and R11 are defined as above, further characterized in that said reaction is carried out in the presence of a Lewis acid, wherein said Lewis acid is an iron chloride.
A process for producing an optically active tartaric acid ester, said process comprising performing diastereomer resolution on a tartaric acid ester represented by the formula (XI) below
- where R8 and R9 are identical or different, each being selected from the group consisting of a C1-4 alkyl group, an alkoxyl group, a phenyl group, a C1-4 alkylcarbonyl group, or an unsubstituted or substituted arylcarbonyl group with the substituent being a C1-4 alkyl group and a halogen atom;
- R10 and R11 are different, each being selected from the group consisting of an unsubstituted or substituted C1-4 alkyl group, an unsubstituted or substituted phenyl group, with the substituent being a C1-4 alkyl group or halogen atom, and an aralkyl group;
- and wherein R10 and R11 may combine to form an alicyclic alkyl group substituted by a C1-4 alkyl group or alkoxyl group, said diastereomer resolution is performed by a process selected from the group consisting of crystallization separation, column separation and simulated moving bed separation.
A tartaric acid ester represented by the formula (XIV) below
- where R14 and R15 are identical or different, each denoting a hydrogen atom, or a C1-4 alkyl group, or a halogen-substituted arylcarbonyl group.
A tartaric acid ester having an optical purity higher than 80% ee, which is represented by the formula (XIV) below
- where R14 and R15 are identical or different, each denoting a hydrogen atom, or a C1-4 alkyl group, or a halogen-substituted arylcarbonyl group.
A process for producing an optically active ketone, comprising reacting a secondary alcohol with an alkali metal hypohalite or alkaline earth metal hypohalite in an aqueous medium, wherein said reaction is carried out in the presence of an aliphatic compound having a partition ratio greater than 1 in water at 20° C. for an alicyclic alcohol as the starting material and further having a solubility that is lower than 5 wt % in water at 40° C., and also in the presence of a mineral acid having a pH less than 3 in an amount of 0.1-2 equivalents for said alicyclic alcohol.
A process for producing an optically active ketone comprising reacting an optically active alicyclic alcohol represented by the formula (XIX) below
- where R16 denotes a C1-4 alkyl group or a C1-4 alkoxyl group which is not connected to that carbon atom to which the hydroxyl group is connected, and n is an integer of 0-3, with an alkali metal hypohalite or alkaline earth metal hypohalite in an acid aqueous solution, thereby producing an optically active alicyclic ketone represented by the formula (XX) below
- where R16 denotes a C1-4 alkyl group or a C1-4 alkoxyl group, and n is an integer of 2-5, rendering said reaction solution basic after the completion of said reaction, thereby producing a stable, optically active alicyclic ketone represented by the formula (XXI) below
- where R16 denotes a C1-4 alkyl group or C1-4 alkoxyl group, and n is an integer of 2-5.
A method for storing an optically active α-ketone which comprises the step of keeping the halogen ion content in the optically active α-substituted ketone below 500 ppm when measured by potentiometric titration after heating under reflux with 1N aqueous solution of sodium hydroxide.
A method for storing an optically active α-ketone which comprises keeping the optically active α-substituted ketone away from oxygen, metal, an acid, or a base.
A method for stabilizing an optically active α-substituted ketone which comprises bringing an optically active α-substituted ketone represented by the formula (XXV) below into contact with an inorganic oxide compound, wherein said optically active α-ketone has the formula:
- where
- R18 and R19 each denote:
- (i) a C1-8 aralkyl group;
- (ii) an identical or different unsubstituted or substituted C6-12 aryl group or aralkyl group, with the substituent being a C1-4 alkyl group, alkoxyl group, or halogen;
- R18 and R19 may combine together to form an alkyl ring;
- and wherein R20 denotes a C1-4 alkyl group, alkoxyl group, or halogen.
Dependencies are inferred from the claim text.