CN103172504A - 2,7-二甲基-2,4,6-辛三烯-1,8-二醛的合成方法 - Google Patents
2,7-二甲基-2,4,6-辛三烯-1,8-二醛的合成方法 Download PDFInfo
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- CN103172504A CN103172504A CN2011104402151A CN201110440215A CN103172504A CN 103172504 A CN103172504 A CN 103172504A CN 2011104402151 A CN2011104402151 A CN 2011104402151A CN 201110440215 A CN201110440215 A CN 201110440215A CN 103172504 A CN103172504 A CN 103172504A
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- dialdehyde
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- AYODHZHFDRRQEZ-UHFFFAOYSA-N 2,7-dimethylocta-2,4,6-trienedial Chemical compound O=CC(C)=CC=CC=C(C)C=O AYODHZHFDRRQEZ-UHFFFAOYSA-N 0.000 title abstract 3
- 238000001308 synthesis method Methods 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010189 synthetic method Methods 0.000 claims abstract description 11
- BWDYLUMZXQQYHK-UHFFFAOYSA-N 1,1,3-triethoxy-2-methylbutane Chemical compound CCOC(C)C(C)C(OCC)OCC BWDYLUMZXQQYHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims abstract description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 4
- 229950009390 symclosene Drugs 0.000 claims abstract description 4
- XDHOEHJVXXTEDV-HWKANZROSA-N (e)-1-ethoxyprop-1-ene Chemical compound CCO\C=C\C XDHOEHJVXXTEDV-HWKANZROSA-N 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
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- 239000003054 catalyst Substances 0.000 abstract description 2
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- RNEGNIRUYATIKH-UHFFFAOYSA-N 1-chloro-4,4-diethoxy-3-methylbut-1-ene Chemical compound CCOC(OCC)C(C)C=CCl RNEGNIRUYATIKH-UHFFFAOYSA-N 0.000 abstract 2
- OCOMLLBTVKVLIO-UHFFFAOYSA-N 1-methoxy-2-methylbuta-1,3-diene Chemical compound COC=C(C)C=C OCOMLLBTVKVLIO-UHFFFAOYSA-N 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- MWSYUAWCPRRTJL-UHFFFAOYSA-N 2,3,8,9-tetramethyldeca-3,5,7-triene Chemical compound CC(C)C(C)=CC=CC=C(C)C(C)C MWSYUAWCPRRTJL-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 150000003003 phosphines Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 45
- 229910052799 carbon Inorganic materials 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000002994 raw material Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- 150000001241 acetals Chemical class 0.000 description 10
- 229960004756 ethanol Drugs 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
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- 238000007792 addition Methods 0.000 description 5
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 150000004795 grignard reagents Chemical class 0.000 description 4
- LPDDKAJRWGPGSI-UHFFFAOYSA-N (3-methyl-4-oxobut-2-enyl) acetate Chemical compound CC(=O)OCC=C(C)C=O LPDDKAJRWGPGSI-UHFFFAOYSA-N 0.000 description 3
- QHMVQKOXILNZQR-UHFFFAOYSA-N 1-methoxyprop-1-ene Chemical compound COC=CC QHMVQKOXILNZQR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 238000003512 Claisen condensation reaction Methods 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- FDSDTBUPSURDBL-LOFNIBRQSA-N canthaxanthin Chemical compound CC=1C(=O)CCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)CCC1(C)C FDSDTBUPSURDBL-LOFNIBRQSA-N 0.000 description 2
- 235000021466 carotenoid Nutrition 0.000 description 2
- 150000001747 carotenoids Chemical class 0.000 description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 2
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- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
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- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 235000019155 vitamin A Nutrition 0.000 description 2
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- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 1
- 229940122361 Bisphosphonate Drugs 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- OOUTWVMJGMVRQF-DOYZGLONSA-N Phoenicoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)C(=O)C(O)CC1(C)C)C=CC=C(/C)C=CC2=C(C)C(=O)CCC2(C)C OOUTWVMJGMVRQF-DOYZGLONSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
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- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 1
- 229940022405 astaxanthin Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 description 1
- 229960002747 betacarotene Drugs 0.000 description 1
- 235000012682 canthaxanthin Nutrition 0.000 description 1
- 239000001659 canthaxanthin Substances 0.000 description 1
- 229940008033 canthaxanthin Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 238000006462 rearrangement reaction Methods 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- SRJQTHAZUNRMPR-UYQKXTDMSA-N spinosyn A Chemical compound O([C@H]1CCC[C@@H](OC(=O)C[C@H]2[C@@H]3C=C[C@@H]4C[C@H](C[C@H]4[C@@H]3C=C2C(=O)[C@@H]1C)O[C@H]1[C@@H]([C@H](OC)[C@@H](OC)[C@H](C)O1)OC)CC)[C@H]1CC[C@H](N(C)C)[C@@H](C)O1 SRJQTHAZUNRMPR-UYQKXTDMSA-N 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Classifications
-
- 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
- C07C45/52—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 by dehydration and rearrangement involving two hydroxy groups in the same molecule
-
- 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
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/324—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a phosphorus atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
本发明提供了2,7-二甲基-2,4,6-辛三烯-1,8-二醛的合成方法,所述合成方法包括如下步骤:(1)乙醛二乙基乙缩醛与乙基(1-丙烯基)醚在催化剂的作用下加成得到1,1,3-三乙氧基-2-甲基-丁烷;(2)1,1,3-三乙氧基-2-甲基-丁烷在异喹啉和对甲苯磺酸催化作用下裂解合成得到1-甲氧基-2-甲基-1,3-丁二烯;(3)1-甲氧基-2-甲基-1,3-丁二烯溶在无水乙醇溶剂中与相转移催化剂十六烷基三甲基溴化铵和氯化试剂三氯异氰尿酸合成生成4,4-二乙氧基-3-甲基-1-氯丁烯;(4)4,4-二乙氧基-3-甲基-1-氯丁烯与三苯基膦成盐合成得到膦盐;和(5)膦盐在双氧水作用下并用碳酸钠溶液缩合生成1,1,8,8-四甲基-2,7-二甲基-2,4,6-辛三烯;再在酸性条件下水解合成2,7-二甲基-2,4,6-辛三烯-1,8-二醛。本发明的工艺路线简捷,操作简单,条件温和,收率良好,极具工业价值。
Description
技术领域
本发明涉及一种2,7-二甲基-2,4,6-辛三烯-1,8-二醛的合成生产方法。
背景技术
2,7-二甲基-2,4,6-辛三烯-1,8-二醛,简称十碳双醛,通常为淡黄色粉末状固体,熔点157.0~159.0℃,易溶于甲醇、二氯甲烷,溶于石油醚、乙酸乙酯,微溶于水。十碳双醛无特殊气味,常温下稳定,与氧化剂混放容易变质,通常与空气隔离保存。是合成类胡萝卜素系列化合物(如β-胡萝卜素,角黄素和虾青素,番茄红素等)的关键中间体,随着类胡萝卜素的应用日益广泛,十碳双醛的合成工艺研究显得尤为有重要。
文献报道的合成方法主要有以下几种:路线1:以呋喃为起始原料,与甲醇经过两步加成得到1,1,4,4-四甲氧基-2-丁烯,此双缩醛化合物在路易斯酸催化下与丙烯基甲醚缩合反应得到C10骨架,再经碱处理消除甲醇形成双键得到产物。此路线的技术关键是溴素价格高,毒性大,且化学性质活泼不稳定,其与缩醛的加成反应中副反应较多,例如加成的产物仍然是双缩醛结构,可以进一步与丙烯基甲醚缩合发生调聚反应形成多聚物,这一步反应的控制和分离技术是整条路线的关键。具体反应方程式见反应式1(十碳双醛的合成路线1)。
反应式1
路线2:以1-乙氧基-1-丙烯为起始原料,与原甲酸三乙酯在路易斯酸催化下加成得到1,1,3,3-四乙氧基-2-甲基丙烷,在酸作用下消除一分子乙醇形成2-甲基-3-乙氧基-2-丁烯醛化合物,与乙炔双格氏试剂加成,再脱水形成烯键,三键部分氢化形成双键,最后脱保护,共七步反应合成十碳双醛,该工艺反应步骤长,主要是前三步反应控制较难。十碳双醛总收率只有21%。具体反应方程式见反应式2(十碳双醛的合成路线2)。
反应式2
路线3:以合成维生素A的原料4-乙酰氧基-2-甲基-2-丁烯-1-醛(简称五碳醛)为起始原料,首先用新戊二醇形成缩醛保护物,再碱水解,得到的羟基化合物卤代,与硫化钠反应形成硫醚化合物,硫醚 经氧化变成亚砜,再与连二亚硫酸钠反应脱硫双聚缩合得到,具体反应方程式见反应式3(十碳双醛的合成路线3)。
反应式3
路线4:以苯亚磺酸钠作连接剂,与两分子的2-(3-氯-1-甲基-1-丙烯基)-5,5-二甲基-1,3-二噁烷反应得到砜化合物,再通过强碱消除苯磺基得到十碳双醛。其实所用原料氯化物也是同路线3一样,需要从合成维生素A的原料4-乙酰氧基-2-甲基-2-丁烯-1-醛经过缩醛保护、碱水解、卤代三步反应得到。此路线反应收率较低,总收率只有15%。具体反应方程式见反应式4(十碳双醛的合成路线4)。
反应式4
路线5:丙醛与甲酸甲酯进行Claisen缩合反应,再酯化,得到2-甲基-3-烷氧基-2-丙烯醛,后面几步反应与路线2基本上一样,也是与乙炔双格氏试剂加成,还原三键成双键,再脱水形成共轭双键得到十碳双醛。具体反应方程式见反应式5(十碳双醛的合成路线5)。
反应式5
路线6::以4-乙酰氧基-2-甲基-2-丁烯醛为原料,经醛基保护、酯交换、氧化合成3-(5,5-二甲基-1,3-二嗯烷-2-基)-2-丁烯醛;采用氯化亚铜、1-氧自由基-2,2,6,6-四甲基-4-羟基-哌啶(TEMPO)催化氧化2-(3-羟基-甲基-丙烯基)-5,5-二甲基-1,3-二噁烷合成3-(5,5-二甲基-1,3-二嗯烷-2-基)-2-丁烯醛;2-(3-羟基-1-甲基-1-丙烯基)-5,5-二甲基-1,3-二嗯烷经过氯化合成2-(3-氯-1-甲基-1-丙烯基)-5,5-二甲基-1,3-二嗯烷;3-(5,5-二甲基-1,3-二嗯烷-2-基)-2-丁烯醛、2-(3-氯-1-甲基-1-丙烯基)-5,5-二甲基-1,3-二嗯烷与亚磷酸三乙酯一锅法工艺制得十碳三烯双醛。具体反应方程式见反应式6(十碳双醛的合成路线6)。
反应式6
路线7:以1,4-二卤-2-丁烯为原料,经Abrozov重排反应得到双膦酸酯化合物,再与丙酮醛缩二甲醇进行Wittig-Horner反应、脱保护基得到C10双醛,总收率报道有39%[113,121],不足之处是原料1,4-二氯-2-丁烯或1,4-二溴-2-丁烯未见大规模国产化。具体反应方程式见反应式7(十碳双醛的合成路线7)。
反应式7
路线8:新和成股份有限公司对十碳烯醛的合成方法作出了改进,反式-1,4-二氯-2-丁烯为起始原料,经格氏反应、缩合反应与酸性水解反应合成2,7-二甲基-2,4,6-辛三烯-1,8-二醛(十碳烯醛)。具体反应方程 式见反应式8(十碳双醛的合成路线8)。
反应式8
分析以上诸多路线,路线1用到污染和毒性大的液溴,丙烯基甲醚原料化学性质活泼不稳定,很容易产生过氧化物产生***等危险,路线2需要用到乙炔双格式试剂和三键部分氢化,总收率只有21%,不适合工业化生产。路线3和4都要用到4-乙酰氧基-2-甲基-2-丁烯-1-醛作为起始原料,成本高,原子经济性差,这一很大缺点是路线3和4工业化的最大障碍。路线5中,甲酸酯和丙醛,乙炔,硫酸二甲酯都是常规化工原料,然而丙醛与甲酸酯发生Claisen缩合反应的同时更易发生自身的Adol羟醛缩合反应,由于产物少,自身缩合的副产物多,而且产物和原料以及副产物的分离也存在着较大的困难。路线6中,用到TEMPO价格高,用DNF做溶剂具有原料与产物分离困难。路线7和路线8均采用1,4-二氯丁烯为原料,通过witting和格氏反应与丙酮醛缩二甲醇缩合,但是制作丙酮醛缩二甲醇成本高,1,4-二氯丁烯制备的双格式试剂及其不稳定,不适合在生产中推广。
发明内容
本发明是通过对以上路线的综合和分析后,提出了一条全新的十 碳双醛的合成方法。具体反应方程式见反应式9(十碳双醛的合成路线9)。
反应式9
根据本发明,2,7-二甲基-2,4,6-辛三烯-1,8-二醛的合成方法包括如下步骤:(1)乙醛二乙基乙缩醛(简称乙缩醛)与乙基(1-丙烯基)醚(简称丙烯基***)在催化剂的作用下在-10℃~0℃温度下加成反应得到1,1,3-三乙氧基-2-甲基-丁烷;其中,所述催化剂为三氯化铁或三氯化铝;其中,乙醛二乙基乙缩醛是根据霍夫曼-拉罗奇有限公司的专利ZL97115390.6制备而得;(2)1,1,3-三乙氧基-2-甲基-丁烷在异喹啉和对甲苯磺酸催化作用下在180-200℃温度下裂解合成得到1-甲氧基-2-甲基-1,3-丁二烯;而在霍夫曼-拉罗奇有限公司的专利发明(ZL97115390.6)中采用硅酸铝小球催化剂,在高温下实现裂解合成1-甲氧基-2-甲基-1,3-丁二烯,其转化率只有41%,选择性为90%;(3)1-甲氧基-2-甲基-1,3-丁二烯溶在无水乙醇溶剂中与相转移催化剂十六烷基三甲基溴化铵和氯化试剂三氯异氰尿酸在-5~0℃温度下合成生成4,4-二乙氧基-3-甲基-1-氯丁烯;和(4)4,4-二乙氧基-3-甲基-1-氯丁烯与三苯基膦在60~65℃温度下成盐合成得到膦盐;和(5)膦盐在双氧水作用下在0~5℃温度下缩合,并用碳酸钠溶液维持体系pH=8~10生成1,1,8,8-四甲基-2,7-二甲基-2,4,6-辛三烯;再在酸性条 件下水解合成2,7-二甲基-2,4,6-辛三烯-1,8-二醛。
优选地,步骤(1)中,在惰性气体保护下进行加成反应。步骤(3)中,1-甲氧基-2-甲基-1,3-丁二烯溶在无水乙醇溶剂中与相转移催化剂时,可以添加乙酸钾。步骤(5)中,双氧水的浓度为35wt.%,碳酸钠溶液的浓度为10wt.%,所述酸性条件为5wt.%的硫酸水溶液200mL和乙醇100mL。
本发明的工艺路线简捷,操作简单,条件温和,收率良好,极具工业价值。
具体实施方式
现结合所附较佳实施例详细说明如下,所说明的较佳实施例仅用于说明本发明的技术方案,并非限定本发明。
实施例1
在氮气保护下,500ml四口烧瓶中投入乙醛二乙基乙缩醛(简称:乙缩醛)83g,三氯化铁1g,用冷冻至-5℃,控制温度在-5~0℃,缓慢滴加乙缩醛94g与丙烯基***86g(0.945mol)的混合液,滴毕继续搅拌10min,GC分析反应完全。在反应液中加入氢氧化钠水溶液中和反应液至pH=7~8,分层,油层用水洗涤后加入无水硫酸钠干燥,加热温度到60℃;回收大部分乙缩醛后,用真空精馏方法得到1,1,3-三乙氧基-2-甲基-丁烷156.1g,含量达到98.5%,以丙烯基***计收率81%。
1HNMR(400MHz,CDCl3)δ(ppm):0.606(d,J=6.8Hz,3H,(CH)2CHCH* 3);0.798-0.964(m,12H,4CH3);1.653-1.675(m,1H, (CH)2CH*CH3);3.104-3.306(m,6H,3OCH* 2CH3);3.341-3.436(m,1H,OCH*CH3);4.193(d,J=5.6Hz,1H,OCH*O)。
13CNMR(100MHz,CDCl3)δ(ppm):8.37,14.95,15.20,15.54,16.89,40.99,62.01,62.31,63.16,75.09,104.11。
DEPT135(100MHz,CDCl3)δ(ppm):8.36,14.95,15.20,15.54,16.89,40.98,62.01(D),62.31(D),63.16(D),75.09,104.10。
实施例2
在氮气保护下,500ml四口烧瓶中投入乙醛二乙基乙缩醛(简称:乙缩醛)236g,三氯化铝1g,用冷冻至-10℃,控制温度在-10℃~-5℃,缓慢滴加乙缩醛118g与丙烯基***86g(0.945mol)的混合液,滴毕继续搅拌10min,GC分析反应完全。在反应液中加入碳酸氢钠饱和水溶液中和反应液至PH=7,分层,油层用水洗涤后加入无水硫酸镁干燥,加热温度50℃;回收大部分乙缩醛后,用真空精馏方法得到1,1,3-三乙氧基-2-甲基-丁烷169.6g,含量达到97.2%,以丙烯基***计收率88%。
实施例3
在500mL三口烧瓶中,加入异喹啉12.7g,对甲苯磺酸0.69g。磁力搅拌,外温加热到220-240℃,此时内温到180-200℃,滴加1,1,3-三乙氧基-2-甲基-丁烷约139.5g(0.684mol),边滴加边蒸出产物。用时6.5小时滴完,共收集物色液体125g。(GC分析乙醇34%,产物63%),常压蒸馏1-甲氧基-2-甲基-1,3-丁二烯,蒸出大部分乙醇。得 底料:乙醇10%,丁二烯85%。油温100℃减压精馏得产物74.5g,97.2%。
1HNMR(400MHz,CDCl3)δ(ppm):1.268(t,J=7.2Hz,3H,OCH2CH* 3);1.746(s,3H,CH2=CCH* 3);3.787-3.861(m,2H,OCH* 2CH3);4.797-4.823,4.942-4.985(m,2H,C=CH2);6.193(s,1H,OCH*=CH);6.265(dd,J1=10.4Hz,J2=17.2Hz,1H,OCH*=CH)。
13CNMR(100MHz,CDCl3)δ(ppm):8.72,15.19,67.95,107.57,114.47,136.81,147.77。
DEPT135(100MHz,CDCl3)δ(ppm):8.72,15.19,67.9(D)5,107.57(D),136.81,147.77。
实施例4
在实施例3的基础上,将烧瓶加热到220-240℃,此时内温到180-200℃,滴加1,1,3-三乙氧基-2-甲基-丁烷约139.5g(0.684mol),边滴加边蒸出产物。用时5小时滴完,共收集物色液体130g。(GC分析乙醇35%,产物62%),常压蒸馏1-甲氧基-2-甲基-1,3-丁二烯,蒸出大部分乙醇。得底料:乙醇10%,丁二烯85%。油温100℃减压精馏得产物75g,产率97.9%。
实施例5
1000ml反应瓶,加入1-甲氧基-2-甲基-1,3-丁二烯46.8g(0.418mol),无水乙醇500mL,十六烷基三甲基溴化铵2.0g,乙酸钾20g,甲苯200mL,冷冻,当内温降低到-5~0℃,开始缓慢加入固 体三氯异氰尿酸90g(0.387mol),待固体溶解,溶液变成乳白色。然后在室温搅拌30min,停止反应,加入饱和碳酸氢钠中和,正戊烷萃取三次,油层用水洗涤2二次,用无水硫酸钠干燥,过滤,除去正戊烷,精馏收集,得4,4-二乙氧基-3-甲基-1-氯丁烯60g,收率74.6%,含量95.6%。(该步骤产物很不稳定,需要很快用于下步反应,故没有进一步检测)
实施例6
4,4-二乙氧基-3-甲基-1-氯丁烯60g(0.311mol),三苯基膦100g(0.382mol),甲醇250mL混合,在60~65℃条件下保温反应2小时,将反应混合物加入100mL去离子水,用500mL正己烷萃取分层3~5次,正己烷层回收可套用,萃取出的未反应三苯基膦可结晶套用。含有膦盐的甲醇溶液回收甲醇,用1000mL二氯甲烷萃取,回收溶剂后得到膦盐140g(0.308mol),收率99%。HPLC分析含量95%。
1HNMR(400MHz,CDCl3)δ(ppm):1.162(t,J=7.2Hz,6H,2OCH2CH* 3);1.396(s,3H,CH2=CCH* 3);3.613-3.666(m,4H,2OCH* 2CH3);5.195(dd,J1=8.0Hz,J2=16.8Hz,2H,CH2P);6.520-6.538(m,1H,CH*C=CH);7.521-7.572(m,1H,CHC=CH*);7.637-7.696,73767-7.808,7.851-7.904(m,15H,Ph)。
13CNMR(100MHz,CDCl3)δ(ppm):10.04,10.06;18.37;25.57,26.07;58.07;117.86,118.91;130.46,130.48;130.57,130.61;133.49,133.53;135.45,135.48;146.01,146.13。
DEPT135(100MHz,CDCl3)δ(ppm):10.04,10.06;18.37;25.56, 26.06;58.07;130.46,130.48;130.57,130.61;133.49,133.53;135.45,135.48.
实施例7
膦盐40g(0.088mol)用200mL二氯甲烷溶解,加入水200mL,降温至0℃,控制温度在0~5℃,滴加35%双氧水10g(0.103mol),约1h内加完,滴加过程中滴加10%碳酸钠溶液维持体系pH=8~10。室温继续搅拌1小时,静置分层,红色有机层用水200ml洗涤,用10%的亚硫酸100mL洗涤,分层。回收干二氯甲烷,加入5%的硫酸水溶液200mL,乙醇100mL,于40℃搅拌5小时,过滤,水洗,用95%乙醇200mL,加热回流0.5小时。冷却0℃,过滤,减压烘干得到淡黄色针状结晶,11.5g,收率80%。
1HNMR(400MHz,CDCl3)δ(ppm):1.920(s,6H,2CH3);6.730~7.551(m,4H,2CH=CH);9.542(dd,J1=8.8Hz,J2=16.8Hz,2H,2CHO)。
13CNMR(100MHz,CDCl3)δ(ppm):9.7;130.4;140.9;146.2;194.7。
需要声明的是,上述发明内容及具体实施方式意在证明本发明所提供技术方案的实际应用,不应解释为对本发明保护范围的限定。本领域技术人员在本发明的精神和原理内,当可作各种修改、等同替换、或改进。
Claims (4)
1.2,7-二甲基-2,4,6-辛三烯-1,8-二醛的合成方法,所述合成方法包括如下步骤:
(1)乙醛二乙基乙缩醛与乙基(1-丙烯基)醚在催化剂的作用下在-10℃~0℃温度下加成反应得到1,1,3-三乙氧基-2-甲基-丁烷;其中,所述催化剂为三氯化铁或三氯化铝;
(2)1,1,3-三乙氧基-2-甲基-丁烷在异喹啉和对甲苯磺酸催化作用下在180-200℃温度下裂解合成得到1-甲氧基-2-甲基-1,3-丁二烯;
(3)1-甲氧基-2-甲基-1,3-丁二烯溶在无水乙醇溶剂中与相转移催化剂和氯化试剂在-5~0℃温度下合成生成4,4-二乙氧基-3-甲基-1-氯丁烯;其中,相转移催化剂为十六烷基三甲基溴化铵,氯化试剂为三氯异氰尿酸;
(4)4,4-二乙氧基-3-甲基-1-氯丁烯与三苯基膦在60~65℃温度下成盐合成得到膦盐;和
(5)膦盐在双氧水作用下在0~5℃温度下缩合,并用碳酸钠溶液维持体系pH=8~10生成1,1,8,8-四甲基-2,7-二甲基-2,4,6-辛三烯;再在酸性条件下水解合成2,7-二甲基-2,4,6-辛三烯-1,8-二醛。
2.如权利要求1所述的合成方法,其中,步骤(1)中,在惰性气体保护下进行加成反应。
3.如权利要求1所述的合成方法,其中,步骤(3)中,1-甲氧基-2-甲基-1,3-丁二烯溶在无水乙醇溶剂中与相转移催化剂时,添加乙酸钾。
4.如权利要求1所述的合成方法,其中,步骤(5)中,双氧水的浓度为35wt.%,碳酸钠溶液的浓度为10wt.%,所述酸性条件为5wt.%的硫酸水溶液200mL和乙醇100mL。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5107030A (en) * | 1991-03-04 | 1992-04-21 | Loyola University Of Chicago | Method of making 2,7-dimethyl-2,4,6-octatrienedial and derivatives thereof |
US5276209A (en) * | 1991-07-19 | 1994-01-04 | Basf Aktiengesellschaft | Preparation of polyenes |
US5471005A (en) * | 1994-11-18 | 1995-11-28 | Loyola University Of Chicago | Method of making 2,7-dimethyl-2,4,6-octatrienedial, a key intermediate in the commercial syntheses of various carotenoids |
CN1178783A (zh) * | 1996-08-19 | 1998-04-15 | 霍夫曼-拉罗奇有限公司 | γ-惕各酸醛的制备方法 |
CN1324345A (zh) * | 1998-11-06 | 2001-11-28 | 具相湖 | 含有多烯链结构的化合物和其制备方法 |
WO2003072734A2 (en) * | 2002-02-25 | 2003-09-04 | Diffusion Pharmaceuticals Llc | Bipolar trans carotenoid salts and their uses |
CN1660742A (zh) * | 2004-12-30 | 2005-08-31 | 浙江大学 | 2-烷氧基丙烯的合成新工艺 |
CN1918099A (zh) * | 2004-02-10 | 2007-02-21 | 巴斯福股份公司 | 制备2,7-二甲基辛-2,4,6-三烯二醛的方法 |
CN101234957A (zh) * | 2008-03-11 | 2008-08-06 | 浙江大学 | 一种2,7-二甲基-2,4,6-辛三烯-1,8-二醛的合成方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6153769A (en) * | 1997-11-27 | 2000-11-28 | Roche Vitamins Inc. | Manufacture of polyene aldehydes |
CN102180774B (zh) * | 2011-04-02 | 2013-06-12 | 绍兴文理学院 | 一种c-14烯醇醚的制备方法 |
-
2011
- 2011-12-26 CN CN201110440215.1A patent/CN103172504B/zh active Active
-
2012
- 2012-12-10 EP EP12863035.7A patent/EP2799420B1/en active Active
- 2012-12-10 WO PCT/CN2012/001666 patent/WO2013097284A1/zh active Application Filing
- 2012-12-10 US US14/369,164 patent/US9187394B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5107030A (en) * | 1991-03-04 | 1992-04-21 | Loyola University Of Chicago | Method of making 2,7-dimethyl-2,4,6-octatrienedial and derivatives thereof |
US5276209A (en) * | 1991-07-19 | 1994-01-04 | Basf Aktiengesellschaft | Preparation of polyenes |
US5471005A (en) * | 1994-11-18 | 1995-11-28 | Loyola University Of Chicago | Method of making 2,7-dimethyl-2,4,6-octatrienedial, a key intermediate in the commercial syntheses of various carotenoids |
CN1178783A (zh) * | 1996-08-19 | 1998-04-15 | 霍夫曼-拉罗奇有限公司 | γ-惕各酸醛的制备方法 |
CN1324345A (zh) * | 1998-11-06 | 2001-11-28 | 具相湖 | 含有多烯链结构的化合物和其制备方法 |
WO2003072734A2 (en) * | 2002-02-25 | 2003-09-04 | Diffusion Pharmaceuticals Llc | Bipolar trans carotenoid salts and their uses |
CN1918099A (zh) * | 2004-02-10 | 2007-02-21 | 巴斯福股份公司 | 制备2,7-二甲基辛-2,4,6-三烯二醛的方法 |
CN1660742A (zh) * | 2004-12-30 | 2005-08-31 | 浙江大学 | 2-烷氧基丙烯的合成新工艺 |
CN101234957A (zh) * | 2008-03-11 | 2008-08-06 | 浙江大学 | 一种2,7-二甲基-2,4,6-辛三烯-1,8-二醛的合成方法 |
Non-Patent Citations (2)
Title |
---|
杨泽慧,等: "2,7-二甲基-2,4,6-辛三烯-1,8-二醛合成新工艺研究", 《浙江大学学报》, vol. 32, no. 6, 30 November 2005 (2005-11-30) * |
汤丹丹,等: "2,7-二甲基-2,4,6-辛三烯二醛的合成研究", 《化学研究与应用》, vol. 22, no. 9, 30 September 2010 (2010-09-30) * |
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