Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
  • C07D307/935—Not further condensed cyclopenta [b] furans or hydrogenated cyclopenta [b] furans
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
  • C12C11/00—Fermentation processes for beer
  • C12C11/02—Pitching yeast
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/07—Optical isomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T436/00—Chemistry: analytical and immunological testing
  • Y10T436/20—Oxygen containing
  • Y10T436/203332—Hydroxyl containing
  • Y10T436/204165—Ethanol

Definitions

• the present invention relates to an optical resolving reagent comprising a bicyclo[3.3.0]-1-oxaoctane compound or a bicyclo[3.3.0]-1-oxa-6-octene compound and to a method for optically resolving an alcohol with the optical resolving reagent.
• physiologically active substances such as pharmaceuticals, agricultural chemicals, perfumes, and sweeteners comprise a partial structure of alcohol having an asymmetric carbon atom.
• Optical isomers can be present in such a compound.
• Some isomers exhibit physiological activity quite different from others. Therefore, development of a method for separating an optical isomer mixture of an alcohol or a compound having a partial structure of alcohol (hereinafter both simply referred to as “alcohol”) easily and surely has been desired.
• the mixture can rarely be separated into two optical isomers without being influenced by an external optically active factor. Spontaneous resolution or the like rarely occurs. There are no general rules for separating the mixture. Accordingly, in almost all cases, it is highly difficult to assess whether or not an optical isomer mixture of an alcohol can be separated into optically active compounds. The mixture is not easily separated in almost all cases.
• the present invention has been achieved in view of such a situation. Accordingly, the present invention provides a novel optical resolving reagent that can optically resolve an optical isomer mixture of an alcohol, having an asymmetric carbon atom in the molecule, easily and industrially advantageously, and a method for optically resolving an alcohol using the optical resolving reagent.
• an alcohol-addition acetal compound can be obtained at a high yield by reacting an oxaoctane compound having an acetal structure or alkenyl ether structure in the molecule with an alcohol (Tetrahedron Lett., 35, 7785 (1994)).
• the present inventors have applied this reaction to an alcohol having an asymmetric carbon atom in the molecule (optical isomer mixture) to obtain an alcohol-addition acetal compound at a high yield.
• the present inventors have found that an acetal compound obtained as a diastereomer mixture can be separated into individual diastereomers using a convenient separation means and that an optically active alcohol can be isolated from the resulting diastereomers at a high yield.
• a first object of the present invention is to provide an optical resolving reagent comprising at least one of the compounds of the following formula (1) or (2):
• R 1 -R 8 individually represent a hydrogen atom or an alkyl group having 1-20 carbon atoms
• R 9 represents a substituted or unsubstituted alkyl group having 1-20 carbon atoms, substituted or unsubstituted alkenyl group having 1-20 carbon atoms, formyl group, or an acyl group
• R 10 represents an alkyl group having 1-6 carbon atoms, provided that a R 9 group and a OR 10 group are cis-configured.
• the optical resolving reagent of the present invention preferably comprises any one of the compounds in which R 1 -R 8 are individually a hydrogen atom or methyl group, with the compounds having a hydrogen atom for all R 1 -R 8 groups being more preferable.
• the optical resolving reagent of the present invention preferably comprises any one of the compounds in which R 9 is an allyl group or a group that can be derived from an allyl group, and more preferably either an allyl group or diphenylmethyl group.
• a second object of the present invention is to provide a method for optically resolving an alcohol of the formula (3):
• R 11 , R 12 , and R 13 individually represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1-20 carbon atoms, provided that at least one of R 11 , R 12 , and R 13 is not a hydrogen atom, the method comprising:
• R 1 -R 13 are the same as defined above, * represents an asymmetric carbon atom, and a R 9 group and a OC(R 11 )(R 12 )(R 13 ) group are cis-configured,
• a compound in which R 1 -R 8 are individually a hydrogen atom or methyl group is preferably used.
• a compound in which all R 1 -R 8 groups are a hydrogen atom is more preferably used.
• a compound in which R 9 is an allyl group or a group that can be derived from an allyl group is preferably used.
• a compound in which R 9 is an allyl group or diphenylmethyl group is more preferably used.
• the method for optical resolution of the present invention preferably comprises optically resolving an optical isomer mixture of an alcohol having an asymmetric carbon atom in the molecule of the formula (3-1):
• R 11a and R 12a respectively represent the same groups as defined for R 11 and R 12 excluding a hydrogen atom, or an optical isomer mixture of a primary alcohol having an asymmetric carbon atom in the molecule of the formula (3-2):
• R 11b represents a substituted or unsubstituted alkyl group having 1-20 carbon atoms and having an asymmetric carbon atom.
• an acid catalyst is preferably present in the reaction system in the step of reacting any one of the compounds of the above formula (1) or (2) with the alcohol of the formula (3) to obtain the compound of the formula (4).
• an alcohol of the formula, R 14 OH, wherein R 14 is the same as R 10 is more preferably used.
• the method for optical resolution of the present invention preferably comprises collecting the compound of the above formula (1) or (2) to reuse the compound as an optical resolving reagent after the step of obtaining the optically active alcohol of the above formula (3).
• the optical resolving reagent of the present invention comprises at least one of the compounds of the above formula (1) or (2).
• the compound of the above formula (1) or (2) has a (pentacyclic+pentacyclic) skeleton. It is known that a R 9 group and an OR 10 group are cis-configured in a compound having such a skeleton (Tetrahedron Lett., 35, 7785 (1994)). Therefore, if R 1 , R 3 , R 5 , and R 7 are respectively the same as R 2 , R 4 , R 6 , and R 8 , the compound of the above formula (1) and the compound of the above formula (2) can respectively have two optical isomers [(1-1 and 1-2), (2-1 and 2-2)].
• any one of these optical isomers may be used.
• an optical isomer mixture of the compound of the formula (1-1) and the compound of the formula (1-2) or an optical isomer mixture of the compound of the formula (2-1) and the compound of the formula (2-2) may be used as an optical resolving reagent without separating the mixture into individual optical isomers.
• R 1 -R 8 individually represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1-20 carbon atoms.
• the substituted or unsubstituted alkyl group having 1-20 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, and n-decyl group.
• substituent for these groups include a hydroxyl group; alkoxy groups such as a methoxy group and ethoxy group; alkylthio groups such as a methylthio group and ethylthio group; halogen atoms such as a fluorine atom and chlorine atom; and substituted or unsubstituted phenyl groups such as a phenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, and 4-methylphenyl group.
• R 1 -R 8 may respectively have a plurality of the same or different substituents.
• R 1 -R 8 are individually a hydrogen atom or methyl group, since the compound can be easily made available or produced.
• a compound in which all R 1 -R 8 groups are a hydrogen atom is more preferable.
• R 9 represents a substituted or unsubstituted alkyl group having 1-20 carbon atoms, substituted or unsubstituted alkenyl group, formyl group, or acyl group.
• substituted or unsubstituted alkyl group having 1-20 carbon atoms examples include the above substituted or unsubstituted alkyl groups having 1-20 carbon atoms of R 1 -R 8 can be given.
• Examples of the substituted or unsubstituted alkenyl group include an allyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, and 2-butenyl group.
• substituent for these groups include a hydroxyl group; alkoxy groups such as a methoxy group and ethoxy group; alkylthio groups such as a methylthio group and ethylthio group; halogen atoms such as a fluorine atom and chlorine atom; and substituted or unsubstituted phenyl groups such as a phenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, and 4-methylphenyl group.
• acyl group examples include an acetyl group, propionyl group, benzoyl group, 2-chlorobenzoyl group, 4-methylbenzoyl group, and 2,4-dimethoxybenzoyl group.
• R 9 may have a plurality of the same or different substituents.
• R 9 is preferably an allyl group or an alkyl group having 1-3 carbon atoms which may have a substituent that can be derived from an allyl group.
• the “substituent that can be derived from an allyl group” refers to a group which can be derived and synthesized from an allyl group using various chemical reactions. There are no specific limitations to the chemical reaction used inasmuch as the reaction conditions ensure the chemical stability of a bicyclooxaoctane ring. Specific examples of the chemical reaction include a dislocation reaction, reduction reaction, oxidation reaction, and Grignard reaction.
• palladium complexes such as dichlorobis(benzonitrile)palladium can be used as a dislocation catalyst, for example.
• reducing agents such as a metal lithium-ammonium reducing agent, lithium aluminum hydride, diisobutylaluminum hydride, and sodium borohydride can be used.
• a catalytic hydrogenation reduction using hydrogenation catalysts such as palladium-carbon may be employed.
• oxidizing agents such as ozone, manganese dioxide, potassium permanganate, chromic acid, and dichromate can be used.
• various Grignard reaction agents such as methylmagnesium bromide, ethylmagnesium bromide, and phenylmagnesium bromide can be used.
• Examples of the allyl group or the substituent that can be derived from the allyl group include a propyl group; 1-propenyl group; formyl group; 1-hydroxyalkyl groups such as a hydroxymethyl group, 1-hydroxyethyl group, 1-hydroxyisopropyl group, and 1-hydroxydiphenylmethyl group; ⁇ -hydroxyaralkyl groups such as an ⁇ -hydroxybenzyl group; acyl groups such as an acetyl group, propionyl group, and benzoyl group; and aralkyl groups such as a benzyl group and diphenylmethyl group.
• R 9 is more preferably an allyl group or diphenylmethyl group, since a target product can be obtained at a high yield and can exhibit excellent properties as an optical resolving reagent of an alcohol.
• optical isomer mixture of the compound of the formula (1) can be produced according to the method described in Tetrahedron Lett., 35, 7785 (1994), for example.
• a common production route of the mixture is shown as follows.
• X represents a halogen atom
• A represents a protective group for the hydroxyl group such as an acetyl group
• R 1 -R 9 are the same as defined above.
• the compound of the formula (1) can be obtained by reacting a cyclopentanone derivative of the formula (5) with a halide of the formula, AOC(R 7 )(R 8 )C(R 5 )(R 6 )X, in the presence of a base to obtain an intermediate of the formula (6) and reacting the intermediate with an alcohol of the formula, R 10 OH, in the presence of an-acid catalyst such as p-toluenesulfonic acid (p-TsOH).
• p-TsOH p-toluenesulfonic acid
• R 10 herein represents a substituted or unsubstituted alkyl group having 1-6 carbon atoms.
• the substituted or unsubstituted alkyl group having 1-6 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, and n-hexyl group.
• substituent for these groups include alkoxy groups such as a methoxy group and ethoxy group; alkylthio groups such as a methylthio group and ethylthio group; halogen atoms such as a fluorine atom and chlorine atom; and substituted or unsubstituted phenyl groups such as a phenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, and 4-methylphenyl group.
• R 10 may have a plurality of the same or different substituents.
• Specific examples of the compound of the formula (1) include 7-methoxy-8-methyl-bicyclo[3.3.0]-1-oxaoctane, 7-ethoxy-8-methyl-bicyclo[3.3.0]-1-oxaoctane, 7-n-propoxy-8-methyl-bicyclo[3.3.0]-1-oxaoctane, 7-isopropoxy-8-methyl-bicyclo[3.3.0]-1-oxaoctane, 7-t-butoxy-8-methyl-bicyclo[3.3.0]-1-oxaoctane, 7-methoxy-8-ethyl-bicyclo[3.3.0]-1-oxaoctane, 7-ethoxy-8-ethyl-bicyclo[3.3.0]-1-oxaoctane, 7-n-propoxy-8-ethyl-bicyclo[3.3.0]-1-oxaoctane, 7-iso
• the compound of the above formula (2) can be derived from the compound of the formula (1) according to the following reaction equation (see Tetrahedron Lett., 35, 7785 (1994)). The reaction is known to proceed while the steric configuration of the compound is maintained.
• R 1 -R 10 are the same as defined above.
• the compound of the formula (2) can be obtained by reacting the compound of the formula (1) with acetyl chloride in an inert solvent to obtain an intermediate (not isolated) of the formula (7) and reacting the intermediate with t-butyl alcohol (t-BuOH) and triethylamine (Et 3 N).
• Examples of the compound of the formula (2) include 8-methyl-bicyclo[3.3.0]-1-oxa-6-octene, 8-ethyl-bicyclo[3.3.0]-1-oxa-6-octene, 8-n-propyl-bicyclo[3.3.0]-1-oxa-6-octene, 8-allyl-bicyclo[3.3.0]-1-oxa-6-octene, 8-benzyl-bicyclo[3.3.0]-1-oxa-6-octene, 8-diphenylmethyl-bicyclo[3.3.0]-1-oxa-6-octene, 8-(1-propenyl)-bicyclo[3.3.0]-1-oxa-6-octene, 8-methoxymethyl-bicyclo[3.3.0]-1-oxa-6-octene, 8-formyl-bicyclo[3.3.0]-1-oxa-6-octene,
• the method for optical resolution of the present invention comprises (i) a step of reacting a compound of the formula (1) or (2) with an optical isomer mixture of an alcohol having an asymmetric carbon atom in the molecule of the formula (3), (R 11 )(R 12 )(R 13 )COH, to obtain a diastereomer mixture of the formula (4), (ii) a step of separating the resulting diastereomer mixture of the formula (4) into individual diastereomers, and (iii) a step of reacting the separated diastereomers with an alcohol of the formula, R 14 OH, to obtain an optically active alcohol of the formula (3).
• R 11 , R 12 , and R 13 individually represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1-20 carbon atoms, provided that at least one of R 11 , R 12 , and R 13 is not a hydrogen atom.
• substituted or unsubstituted alkyl group having 1-20 carbon atoms examples of the substituted or unsubstituted alkyl group having 1-20 carbon atoms, the specific substituted or unsubstituted alkyl groups having 1-20 carbon atoms given as examples of R 1 -R 8 can be given.
• R 11a refers to the same groups as defined for R 11 excluding a hydrogen atom.
• R 12a refers to the same groups as defined for R 12 excluding a hydrogen atom.
• R 11b represents a substituted or unsubstituted alkyl group having 1-20 carbon atoms and having an asymmetric carbon atom.
• R 11b examples include a 1-methylpropyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-ethylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 1-ethylhexyl group, 2-ethylhexyl group, and 2-propylhexyl group.
• step (i) of reacting an optically active compound of the formula (1) or (2) with an optical isomer mixture of an alcohol of the formula (3) is carried out by mixing and stirring both compounds in a suitable solvent.
• the solvent used for this reaction inasmuch as the solvent is nonprotonic.
• the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, benzonitrile, and dichlorobenzene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane, and petroleum ether; esters such as ethyl acetate, propyl acetate, and butyl acetate; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and 1,1,2-trichloroethane; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; and amides
• organic solvents with a comparatively low boiling point including aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane, and petroleum ether; and halogenated hydrocarbons such as chloroform and carbon tetrachloride.
• aromatic hydrocarbons such as benzene, toluene, and xylene
• aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane, and petroleum ether
• halogenated hydrocarbons such as chloroform and carbon tetrachloride.
• an acid catalyst such as pyridinium p-toluenesulfonate (PPTS), p-toluenesulfonic acid (p-TsOH), or montmorillonite or synthetic zeolite is preferably present in the reaction system.
• the amount of the acid catalyst added is usually 0.0001-1 mol for one mol of the compound of the above formula (1) or (2).
• the reaction is smoothly carried out in the temperature range of ⁇ 20° C. to a boiling point of the solvent used, and more preferably in the temperature range of ⁇ 10° C. to 50° C. The reaction is usually terminated several minutes to dozens of hours after the beginning of reaction.
• the resulting diastereomer mixture of the formula (4) is separated into individual diastereomers.
• This diastereomer mixture can be easily separated into the individual diastereomers by column chromatography using silica gel, alumina, neutral alumina, or the like.
• the eluate for separating the mixture inasmuch as the eluate is an inert solvent to provide a ⁇ Rf value that can allow the mixture to be fully separated into the optical isomers.
• the eluate include n-hexane, n-hexane-benzene, n-hexane-diethyl ether, n-hexane-ethyl acetate, n-hexane-acetone, n-hexane-chloroform, n-hexane-dichloromethane, benzene, benzene-ethyl acetate, benzene-diethyl ether, benzene-chloroform, benzene-dichloromethane, benzene-acetone, acetone, chloroform, and dichloromethane.
• each of the separated optical isomers of the formula (4) is reacted with an alcohol of the formula, R 14 OH, to obtain the optically active alcohols of the formula (3), respectively.
• This reaction can be carried out under the same conditions as in the case of reacting the compound of the above formula (4) with the alcohol of the above formula (3).
• the alcohol (R 14 OH) an alcohol having 1-6 carbon atoms is preferable.
• the alcohol include low-boiling point alcohols such as methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, sec-butanol, and t-butanol.
• R 14 is the same as R 10 is more preferably used. This is because the reaction product can be easily separated and refined after terminating the reaction and the compound of the formula (1) can be repeatedly used as an optical resolving reagent.
• optically active alcohol of the formula (3) separated in this reaction can be isolated using a conventional refining method such as distillation or column chromatography.
• the above reaction proceeds while maintaining the steric configuration of the compound and avoiding a side reaction. Therefore, the compound of the formula (1) or (2) can be collected at a high yield.
• the collected compound of the formula (1) or (2) may be optionally refined and reused as an optical resolving reagent.
• an optical isomer mixture of a compound having a functional group with an asymmetric carbon atom in the molecule and an activated hydrogen, reactive with vinyl ether by an addition reaction can also be optically resolved, wherein examples of such a compound include thiols, carboxylic acids, sulfonic acids, amines, terminal acetylenes, and ⁇ -dicarbonyl compounds.
• the compound of the above formula (1) or (2) can be optically resolved by applying the method for optical resolution of the present invention.
• An outline of the optical resolution is shown in the following scheme.
• R 1 -R 10 and * are the same as defined above, and Ra, Rb, and Rc individually represent a hydrogen atom or a substituted or unsubstituted alkyl group.
• Ra, Rb, and Rc the compounds respectively the same as those given as examples of R 11 , R 12 , and R 13 can be given.
• reaction conditions of the method for optically resolving an alcohol of the present invention can be applied to each reaction in the above scheme.
• the resulting diastereomer mixture of the formula (4′) is separated using a conventional separation means such as silica gel column chromatography.
• the separated diastereomers (4′-1 and 4′-2) are reacted with an alcohol R 14 OH, wherein R 14 is the same as defined for R 10 , to obtain optical isomers (1′-1 and 1′-2) of the compound of the formula (1).
• Optical isomers (2-1 and 2-2) of the compound of the formula (2) can be respectively derived from the resulting optical isomers (1′-1 and 1′-2) using the above-described method.
• a stream of ozone-oxygen was circulated in a solution of 55 g (0.302 mol) of the resulting compound (9) in 275 ml of methylene chloride for 16 hours. After ozonization, excessive ozone was discharged from the reaction solution by circulating dry nitrogen in the solution at the same temperature for 30 minutes. 38.3 ml of methyl sulfide was added to the reaction solution and the mixture was stirred until reaching room temperature. The reaction solution was poured into water and the mixture was extracted with methylene chloride. The organic layer was washed with saturated brine, dried over anhydrous potassium carbonate, and filtered. The filtrate was concentrated under reduced pressure.
• a THF solution (1 M, 40 ml, 40 mmol) of phenylmagnesium bromide was added dropwise to a solution of 4.7 g (19.1 mol) of the resulting compound (12) in 100 ml of THF at 0° C. The mixture was stirred at the same temperature for 30 minutes. The reaction solution was poured into saturated aqueous solution of ammonium chloride and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous potassium carbonate, and filtered. The filtrate was concentrated under reduced pressure.
• the yields of 16a and 16b are respectively 29.1 mg (38%) and 32.2 mg (42%).
• a target product (15a) was obtained from the compound (14a) obtained in Example 5 in the same manner as in Example 3.
• a target product (15b) was obtained from the compound (14b) obtained in Example 6 in the same manner as in Example 3.
• FT-IR (nujor): 3,180, 2,960, 2,880, 1,645, 1,480, 1,460, 1,400, 1,375, 1,330, 1,310, 1,240, 1,195, 1,125, 1,060, 1,025, 960, 948, 920 cm ⁇ 1
• FT-IR (nujor): 3,180, 2,960, 2,880, 1,645, 1,478, 1,460, 1,395, 1,375, 1,325, 1,310, 1,240, 1,195, 1,120, 1,058, 1,025, 960, 948, 920 cm ⁇ 1
• the present invention provides a novel optical resolving reagent which can optically resolve an alcohol having an asymmetric carbon atom in the molecule easily and industrially advantageously.
• the present invention also provides a method for optically resolving an alcohol which can optically resolve a diastereomer mixture of an alcohol that has conventionally been difficult to be optically resolved in the industrial scale easily and industrially advantageously with the optical resolving reagent of the present invention.
• the method for optical resolution of the present invention highly common and highly flexible, can be applied to optical resolution of a broad variety of alcohols.

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• 2002
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