JP5443357B2 - 長鎖アルコールのエステルとその製造方法 - Google Patents
長鎖アルコールのエステルとその製造方法 Download PDFInfo
- Publication number
- JP5443357B2 JP5443357B2 JP2010519962A JP2010519962A JP5443357B2 JP 5443357 B2 JP5443357 B2 JP 5443357B2 JP 2010519962 A JP2010519962 A JP 2010519962A JP 2010519962 A JP2010519962 A JP 2010519962A JP 5443357 B2 JP5443357 B2 JP 5443357B2
- Authority
- JP
- Japan
- Prior art keywords
- ester
- group
- solvent
- long
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 41
- 150000002148 esters Chemical class 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000001298 alcohols Chemical class 0.000 title description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 26
- -1 C 4 alkane Chemical class 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 108090001060 Lipase Proteins 0.000 claims description 14
- 102000004882 Lipase Human genes 0.000 claims description 14
- 239000004367 Lipase Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 235000019421 lipase Nutrition 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 102000004190 Enzymes Human genes 0.000 claims description 10
- 108090000790 Enzymes Proteins 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 125000002714 alpha-linolenoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])/C([H])=C([H])\C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])[H] 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229940087305 limonene Drugs 0.000 claims description 4
- 235000001510 limonene Nutrition 0.000 claims description 4
- 125000002811 oleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000006017 1-propenyl group Chemical group 0.000 claims description 3
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 108090000371 Esterases Proteins 0.000 claims description 3
- 108091005804 Peptidases Proteins 0.000 claims description 3
- 239000004365 Protease Substances 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000003880 polar aprotic solvent Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims 1
- JGPMMRGNQUBGND-UHFFFAOYSA-N idebenone Chemical group COC1=C(OC)C(=O)C(CCCCCCCCCCO)=C(C)C1=O JGPMMRGNQUBGND-UHFFFAOYSA-N 0.000 description 21
- 229960004135 idebenone Drugs 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 4
- 125000002669 linoleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 241000589774 Pseudomonas sp. Species 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 235000020778 linoleic acid Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- LZKSJDMZHXAUNU-UTJQPWESSA-N 10-(4,5-dimethoxy-2-methyl-3,6-dioxocyclohexa-1,4-dien-1-yl)decyl (9z,12z)-octadeca-9,12-dienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCCCCCCCCCCC1=C(C)C(=O)C(OC)=C(OC)C1=O LZKSJDMZHXAUNU-UTJQPWESSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 108010048733 Lipozyme Proteins 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- JBYXPOFIGCOSSB-GOJKSUSPSA-N 9-cis,11-trans-octadecadienoic acid Chemical compound CCCCCC\C=C\C=C/CCCCCCCC(O)=O JBYXPOFIGCOSSB-GOJKSUSPSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010012442 Dermatitis contact Diseases 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 241001661345 Moesziomyces antarcticus Species 0.000 description 1
- 108010084311 Novozyme 435 Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010040865 Skin hyperpigmentation Diseases 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940108924 conjugated linoleic acid Drugs 0.000 description 1
- 208000010247 contact dermatitis Diseases 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000028709 inflammatory response Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000004666 short chain fatty acids Chemical class 0.000 description 1
- 235000021391 short chain fatty acids Nutrition 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
-
- 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
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Genetics & Genomics (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Enzymes And Modification Thereof (AREA)
Description
で表されるエステルを含んでなる組成物に関する。
で表されるエステルの製造方法に関する。
で表される一連の新規長鎖アルコールエステルに関する。
イデベノンリノレエート(1a)(EX00011−037)の製造
イデベノン(2a,R=R1=Me,n=9;547mg;1.6ミリモル)をトルエン10mL中に溶解させた。リノール酸(2.18g;4.9当量)を添加し、次いで4Aモレキュラーシーブ641mg及びNovozym(登録商標)435 309mgを添加した。反応混合物を周囲温度で2日間撹拌した。その時点でtlc分析(酢酸エチル:ヘプタン1:1溶離液)はイデベノンが残っていないことを示した。固形分を濾過によって除去し、沈殿物をトルエンで洗浄した。合した濾液と洗液を減圧濃縮した。残渣をヘプタン(22mL)に溶解させ、メタノール11mLと10%炭酸カリウム水溶液11mLとの混合物で洗浄した。有機層を更にメタノール11mL、飽和炭酸水素ナトリウム4mL及び水7mLの混合物で洗浄した。次いで、有機層を硫酸ナトリウムで乾燥させ、濃縮して、1a(R=R1=Me,n=9)を0.84g(87%)得た。
イデベノン共役リノレエート(1b)(EX00011−037)の製造
イデベノン(2a;499mg;1.48ミリモル)をトルエン10mL中に溶解させた。共役リノール酸(Tonalin(登録商標)FFA;2.07g;5当量)を添加し、次いで4Aモレキュラーシーブ500mg及びNovozym(登録商標)435 300mgを添加した。反応混合物を周囲温度で2日間撹拌した。その時点でtlc分析(酢酸エチル:ヘプタン1:1溶離液)は少量のイデベノンを示した。更に4Aモレキュラーシーブを添加し、混合物を更に2日間撹拌した。その時点で、tlc分析はイデベノンが残っていないことを示した。固形分を濾過によって除去し、沈殿物をトルエンで洗浄した。合した濾液と洗液を減圧濃縮した。残渣をヘプタン(50mL)に溶解させ、メタノールと10%炭酸カリウム水溶液の1:1混合物(50mL,次いで20mL)で2回洗浄した。有機層を更にメタノール15mL、飽和炭酸水素ナトリウム5mL及び水10mLの混合物で洗浄した。次いで、有機層を硫酸ナトリウムで乾燥させ、濃縮して、1bを850mg(96%)得た。
イデベノンとPamolyn200リノール酸のエステル(1c)(EX00011−037)の製造
イデベノン(2a;501mg;1.48ミリモル)をトルエン10mL中に溶解させた。Pamolyn200(登録商標)リノール酸(2.07g;5当量)を添加し、次いで4Aモレキュラーシーブ500mg及びNovozym(登録商標)435 300mgを添加した。反応混合物を周囲温度で2日間撹拌した。その時点でtlc分析(酢酸エチル:ヘプタン1:1溶離液)は少量のイデベノンを示した。更に4Aモレキュラーシーブを添加したが、tlcによって変化は観察されなかった。固形分を濾過によって除去し、沈殿物をトルエンで洗浄した。合した濾液と洗液を減圧濃縮した。残渣をヘプタン(50mL)に溶解させ、メタノールと10%炭酸カリウム水溶液の1:1混合物(50mL)で洗浄した。有機層を更にメタノール15mL、飽和炭酸水素ナトリウム5mL及び水10mLの混合物で洗浄した。次いで、有機層を硫酸ナトリウムで乾燥させ、濃縮して、1bを798mg(90%)得た。
イデベノンオクタノエート(1d)(EX00011−037)の製造
イデベノン(2a;500mg;1.48ミリモル)をトルエン10mL中に溶解させた。オクタン酸(1.07g;5当量)を添加し、次いで4Aモレキュラーシーブ500mg及びNovozym(登録商標)435 300mgを添加した。反応混合物を周囲温度で2日間撹拌した。その時点でtlc分析(酢酸エチル:ヘプタン1:1溶離液)はイデベノンを示さなかった。固形分を濾過によって除去し、沈殿物をトルエンで洗浄した。合した濾液と洗液を減圧濃縮した。真空濃縮によって1dが630mg(92%)得られた。
以下に、本発明の関連態様を列挙する。
態様1.一般式1:
で表されるエステルを含んでなる組成物。
態様2.R 2 のアルキル、アルケニル、ジエニル、トリエニル及びテトラエニルが炭素数約22以下の脂肪族炭化水素基である態様1に記載の組成物。
態様3.炭素数22以下の前記脂肪族炭化水素が、C 1 〜C 6 −アルコキシ、シアノ、C 2 〜C 6 −アルコキシカルボニル、C 2 〜C 6 −アルカノイルオキシ、ヒドロキシ、アリール、ヘテロアリール、チオール、チオエーテル及びハロゲンからなる群から選ばれた1〜3個の基で置換されている態様2に記載の組成物。
態様4.アシル基R 2 −COがリノレオイル、ステアロイル、リノレノイル、共役リノレオイル、パルモイル、オレオイル及びそれらの混合物からなる群から選ばれる態様1に記載の組成物。
態様5.式2:
で表されるエステルの製造方法。
態様6.長鎖酸R 2 COOHを使用し且つ水を前記方法中に除去する態様5に記載の方法。
態様7.R 4 で表される前記C 1 〜C 4 アルキル又はアルケニル基がメチル、エチル、n−プロピル、i−プロピル、n−ブチル、s−ブチル、ビニル、1−プロペニル、2−プロペニル及び2−ブテニルからなる群から選ばれる態様5に記載の方法。
態様8.前記溶媒がエーテル溶媒、芳香族炭化水素溶媒、脂肪族炭化水素溶媒、脂環式炭化水素溶媒、ハロゲン化炭化水素溶媒、極性非プロトン性溶媒及びそれらの混合物からなる群から選ばれる態様5に記載の方法。
態様9.前記溶媒がトルエン、リモネン、アセトニトリル又はそれらの混合物である態様8に記載の方法。
態様10.前記方法を約−100℃及び溶媒の沸点の間の温度で反応させる態様5に記載の方法。
態様11.前記方法を約0〜60℃の温度で反応させる態様10に記載の方法。
態様12.前記方法を約20〜50℃の温度で反応させる態様11に記載の方法。
態様13.前記長鎖酸又は長鎖エステルが、アルコールに基づき、0.85〜20当量の量で存在する態様5に記載の方法。
態様14.前記長鎖酸又は長鎖エステルが1〜10当量の量で存在する態様13に記載の方法。
態様15.使用酵素がプロテアーゼ、リパーゼ及びエステラーゼからなる群から選ばれる態様5に記載の方法。
態様16.前記リパーゼが全細胞、単離された天然酵素の形態又は担体に固定された形態である態様15に記載の方法。
態様17.前記リパーゼがLipase PS、Lipase PS−C、Lipase PS−D、Lipoprime 50T、Lipozyme TL IM及びNovozyme 435からなる群から選ばれる態様15に記載の方法。
態様18.前記エステルを抽出、濾過又は結晶化によって単離する態様5に記載の方法。
態様19.前記エステルを抽出、クロマトグラフィー、蒸留又は結晶化によって精製する態様18に記載の方法。
Claims (12)
- 長鎖酸R2COOHを使用し且つ水を前記方法中に除去する請求項2に記載の方法。
- R4で表される前記C1〜C4アルキル又はアルケニル基がメチル、エチル、n−プロピル、i−プロピル、n−ブチル、s−ブチル、ビニル、1−プロペニル、2−プロペニル及び2−ブテニルからなる群から選ばれる請求項2に記載の方法。
- 前記溶媒がエーテル溶媒、芳香族炭化水素溶媒、脂肪族炭化水素溶媒、脂環式炭化水素溶媒、ハロゲン化炭化水素溶媒、極性非プロトン性溶媒及びそれらの混合物からなる群から選ばれる請求項2に記載の方法。
- 前記溶媒がトルエン、リモネン、アセトニトリル又はそれらの混合物である請求項5に記載の方法。
- 前記方法を−100℃及び溶媒の沸点の間の温度で反応させる請求項2に記載の方法。
- 前記長鎖酸又は長鎖エステルが、アルコールに基づき、0.85〜20当量の量で存在する請求項2に記載の方法。
- 使用酵素がプロテアーゼ、リパーゼ及びエステラーゼからなる群から選ばれる請求項2に記載の方法。
- 前記リパーゼが全細胞、単離された天然酵素の形態又は担体に固定された形態である請求項9に記載の方法。
- 前記エステルを抽出、濾過又は結晶化によって単離する請求項2に記載の方法。
- 前記エステルを抽出、クロマトグラフィー、蒸留又は結晶化によって精製する請求項9に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/890,974 | 2007-08-08 | ||
US11/890,974 US7927855B2 (en) | 2007-08-08 | 2007-08-08 | Esters of long-chain alcohols and preparation thereof |
PCT/US2008/009386 WO2009020586A2 (en) | 2007-08-08 | 2008-08-04 | Esters of long-chain alcohols and preparation therof |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2010535764A JP2010535764A (ja) | 2010-11-25 |
JP5443357B2 true JP5443357B2 (ja) | 2014-03-19 |
Family
ID=39864801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010519962A Expired - Fee Related JP5443357B2 (ja) | 2007-08-08 | 2008-08-04 | 長鎖アルコールのエステルとその製造方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US7927855B2 (ja) |
EP (1) | EP2183257B1 (ja) |
JP (1) | JP5443357B2 (ja) |
CN (1) | CN101772482A (ja) |
BR (1) | BRPI0814159A2 (ja) |
DK (1) | DK2183257T3 (ja) |
ES (1) | ES2403201T3 (ja) |
WO (1) | WO2009020586A2 (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7927855B2 (en) | 2007-08-08 | 2011-04-19 | Eastman Chemical Company | Esters of long-chain alcohols and preparation thereof |
US7872047B2 (en) * | 2008-02-08 | 2011-01-18 | Eastman Chemical Company | Esters of long-chain alcohols and preparation thereof |
US8263094B2 (en) * | 2008-09-23 | 2012-09-11 | Eastman Chemical Company | Esters of 4,5-disubstituted-oxy-2-methyl-3,6-dioxo-cyclohexa-1,4-dienyl alkyl acids and preparation thereof |
US8846723B2 (en) * | 2010-07-29 | 2014-09-30 | Eastman Chemical Company | Esters of O-substituted hydroxy carboxylic acids and preparations thereof |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4407757A (en) * | 1974-05-02 | 1983-10-04 | Takeda Chemical Industries, Ltd. | Aralkyl carboxylic acid compounds |
US4271083A (en) * | 1974-05-02 | 1981-06-02 | Takeda Chemical Industries, Ltd. | 6-Hydroxy-1,4-benzoquinone compounds |
JPS5738744A (en) * | 1980-08-19 | 1982-03-03 | Takeda Chem Ind Ltd | Quinone derivative and its preparation |
JPS62104589A (ja) * | 1985-10-25 | 1987-05-15 | Meito Sangyo Kk | 脂肪酸エステルの製造法 |
JPH01218593A (ja) * | 1988-02-26 | 1989-08-31 | Agency Of Ind Science & Technol | 脂肪酸エステルの合成法 |
JPH11263750A (ja) * | 1998-03-16 | 1999-09-28 | Osaka City | 長鎖不飽和脂肪酸メントールエステルおよび酵素法によるその製造方法 |
JP2000270885A (ja) * | 1999-03-26 | 2000-10-03 | Nippon Suisan Kaisha Ltd | 高度不飽和脂肪酸を含有する構造油脂の製造方法 |
DE19932197A1 (de) | 1999-07-09 | 2001-01-18 | Neudecker Birgit | Topisch anzuwendendes Mittel mit schützender und regenerativer Wirkung |
JP2001161360A (ja) * | 1999-12-10 | 2001-06-19 | Nippon Kayaku Co Ltd | 固定化リパーゼ及びそれを用いる有機化合物の製造方法 |
AR055453A1 (es) | 2004-01-06 | 2007-08-22 | Creactivar S A | Uso de la idebenona en una composicion destinada a ser aplicada sobre la piel y composicion que la comprende |
US20050152857A1 (en) | 2004-01-08 | 2005-07-14 | Pcr Technology Holdings, Lc | Method and preparation for reducing sunburn cell formation in skin |
US20050175559A1 (en) * | 2004-02-10 | 2005-08-11 | Pcr Technology Holdings, Lc | Method and preparation for reducing skin hyperpigmentation |
WO2005079775A1 (en) * | 2004-02-13 | 2005-09-01 | Pcr Technology Holdings, Lc | Method and preparation for reducing irritation and/or inflammatory reaction in human skin |
US7927855B2 (en) | 2007-08-08 | 2011-04-19 | Eastman Chemical Company | Esters of long-chain alcohols and preparation thereof |
US7872047B2 (en) | 2008-02-08 | 2011-01-18 | Eastman Chemical Company | Esters of long-chain alcohols and preparation thereof |
-
2007
- 2007-08-08 US US11/890,974 patent/US7927855B2/en active Active
-
2008
- 2008-08-04 DK DK08795023.4T patent/DK2183257T3/da active
- 2008-08-04 CN CN200880102520A patent/CN101772482A/zh active Pending
- 2008-08-04 EP EP08795023A patent/EP2183257B1/en not_active Not-in-force
- 2008-08-04 BR BRPI0814159-2A2A patent/BRPI0814159A2/pt not_active IP Right Cessation
- 2008-08-04 ES ES08795023T patent/ES2403201T3/es active Active
- 2008-08-04 WO PCT/US2008/009386 patent/WO2009020586A2/en active Application Filing
- 2008-08-04 JP JP2010519962A patent/JP5443357B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
WO2009020586A3 (en) | 2009-04-02 |
EP2183257B1 (en) | 2013-03-20 |
WO2009020586A2 (en) | 2009-02-12 |
BRPI0814159A2 (pt) | 2015-01-06 |
EP2183257A2 (en) | 2010-05-12 |
US7927855B2 (en) | 2011-04-19 |
JP2010535764A (ja) | 2010-11-25 |
ES2403201T3 (es) | 2013-05-16 |
CN101772482A (zh) | 2010-07-07 |
US20090042271A1 (en) | 2009-02-12 |
DK2183257T3 (da) | 2013-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5474556B2 (ja) | 有機溶媒中でリパーゼを用いる短鎖レチニルエステル及び長鎖酸又は長鎖エステルからの長鎖レチニルエステルの製造方法 | |
US9532938B2 (en) | Esters of O-substituted hydroxy carboxylic acids and preparations thereof | |
Galletti et al. | Chemoenzymatic synthesis of (2 S)-2-arylpropanols through a dynamic kinetic resolution of 2-arylpropanals with alcohol dehydrogenases | |
US20100087525A1 (en) | Stereoselective enzymatic synthesis of (s) or (r)-iso-butyl-glutaric ester | |
JP5443357B2 (ja) | 長鎖アルコールのエステルとその製造方法 | |
EP2066798B1 (en) | Process for the preparation of 2-hydroxy carboxylic acids employing bacteria of the genus pseudomonas, rhodococcus or bacillus | |
US8329938B2 (en) | Hydroxyalkanoic acid and hydroxyalkanoice acid oligomer esters of retinol | |
EP0474854B1 (en) | Alcohol-ester separation by recrystallization | |
JP2011511069A (ja) | 長鎖アルコールのエステルおよび皮膚を処置するためのその使用 | |
EP0396447A1 (fr) | Procédé de séparation énantiomériquement sélective des esters des acides halogéno-2 propioniques | |
US20110124064A1 (en) | Esterification process of prostaglandins and analogues thereof | |
JP4789889B2 (ja) | (r)−2−アルキルシクロペンタノンの製造方法 | |
JPH05501883A (ja) | アルコール―エステル分離のための保護ヒドロキシ方法 | |
JP2010505417A (ja) | (3)−アミノ−3−アリールプロピオン酸エステルのn−非保護(r)−エステルの特異的加水分解 | |
JP2012503601A (ja) | 4,5−二置換−オキシ−2−メチル−3,6−ジオキソ−シクロヘキサ−1,4−ジエニルアルキル酸のエステル及びその製造方法 | |
EP0474861A1 (en) | SEPARATION OF AN ALCOHOL AND AN ESTER BY REACTION WITH ACETATE. | |
JP2004350522A (ja) | 光学活性エステルおよび/または光学活性カルボン酸の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110510 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130425 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130514 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20130813 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20130820 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131023 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131119 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131219 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
LAPS | Cancellation because of no payment of annual fees |