CN1980875A - 2-金刚烷醇和2-金刚烷酮的制备方法 - Google Patents
2-金刚烷醇和2-金刚烷酮的制备方法 Download PDFInfo
- Publication number
- CN1980875A CN1980875A CNA2005800227921A CN200580022792A CN1980875A CN 1980875 A CN1980875 A CN 1980875A CN A2005800227921 A CNA2005800227921 A CN A2005800227921A CN 200580022792 A CN200580022792 A CN 200580022792A CN 1980875 A CN1980875 A CN 1980875A
- Authority
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- China
- Prior art keywords
- acid
- adamantanol
- catalyst
- diamantane ketone
- preparing
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- FOWDOWQYRZXQDP-UHFFFAOYSA-N adamantan-2-ol Chemical compound C1C(C2)CC3CC1C(O)C2C3 FOWDOWQYRZXQDP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 title abstract 3
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000003377 acid catalyst Substances 0.000 claims abstract description 19
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011973 solid acid Substances 0.000 claims abstract description 10
- 239000002841 Lewis acid Substances 0.000 claims abstract description 7
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011964 heteropoly acid Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 16
- 235000011007 phosphoric acid Nutrition 0.000 abstract description 14
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 150000003016 phosphoric acids Chemical class 0.000 abstract 1
- 150000003460 sulfonic acids Chemical class 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 12
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 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
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 208000018737 Parkinson disease Diseases 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical class C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003005 anticarcinogenic agent Substances 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- -1 diamantane ketone Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
- C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/453—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
- C07C35/37—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Abstract
公开了由1-金刚烷醇制备2-金刚烷醇和2-金刚烷酮的方法,其中使用至少一种选自路易斯酸和固体酸的酸催化剂作为催化剂,并且同时使用至少一种选自羧酸、磺酸和磷酸的酸。通过该方法可以有效地选择性制备2-金刚烷醇和2-金刚烷酮,而无需使用硫酸作为催化剂。该方法因为节省了处理废酸的劳力,明显缩短了反应时间,所以适合于大规模生产。
Description
技术领域
[0001]
本发明涉及2-金刚烷醇和2-金刚烷酮的制备方法,该方法包括在不用硫酸(基于环境上的考虑)的条件下,使1-金刚烷醇在短时间内发生氧化,从而制备2-金刚烷醇和2-金刚烷酮;2-金刚烷醇和2-金刚烷酮属于金刚烷衍生物,是作为各种药用、农用化学品及工业产品原料的重要中间体。
背景技术
[0002]
金刚烷常被称为篮式(basket-type)化合物,具有高度对称性,其结构与金刚石结构单元相同。作为一种化学物质,它具有诸如以下的特征:(1)分子变形能低而热稳定性高,(2)因其高碳密度而具有高脂溶性,(3)尽管具有升华性但是气味浓度却很低,等等,因此,自二十世纪八十年代起,在药品领域作为帕金森病(Parkinson’s disease)和流感治疗药的原料,引起了人们的广泛关注。然而,近年来,金刚烷衍生物在热稳定性和透明度等方面的特性,在半导体制造用光致抗蚀剂(photo resist)、磁记录媒体、光纤、光学镜头、光盘基材等光学材料领域,耐热塑料、涂料、胶粘剂等功能性材料领域,化妆品、润滑油等领域,都引起了人们的广泛关注,其应用范围一直在不断增大。另外,在制药领域中,对抗癌药、脑功能改善药、神经科疾病用药物、抗病毒药等方面的原料需求也在不断增加。
[0003]
从有效利用碳资源的观点来看,使烃化合物通过氧化转化成醇或酮的技术是一项在工业上非常重要的技术。2-金刚烷酮是各种药用、农用化学品及工业产品原料的重要中间体,浓硫酸中制备2-金刚烷酮的技术是众所周知的。例如,Schlatmann曾报道通过1-金刚烷醇在浓硫酸中于30℃加热12小时,可制得2-金刚烷酮,收率为72%(例如参见非专利文献1)。还知道,通过金刚烷用浓硫酸氧化、再用蒸汽蒸馏纯化,可制得金刚烷酮,收率为47-48%(例如参见非专利文献2)。此外,作为上述方法的改进方法,提出了下述方法:在两级制备法或者三级制备法中进行反应时升高温度(例如参见专利文献1和2)。
然而,尽管2-金刚烷酮的收率已提高到90%,但是这些方法在大规模生产时都会遇到许多挑战,因为大量使用浓硫酸,所以(a)产生大量废酸,(b)需要昂贵的耐腐蚀设备材料,和(c)需要较长反应时间(12-24小时)。
就目前情况看,尚没有不用硫酸作为氧化剂的技术,因此,一直在期待不用硫酸制备2-金刚烷酮技术的出现。
[0004]
[非专利文献1]Tetrahedron:24,5361(1968)。
[非专利文献2]Organic Syntheses 53,8(1973)。
[专利文献1]日本专利特开平H11-189564号公报。
[专利文献2]日本专利特开2003-267906号公报。
发明内容
[0005]
本发明的一个目的是提供一种在非常规短时间内有效地选择性制备2-金刚烷醇和2-金刚烷酮的方法,该方法通过对1-金刚烷醇使用酸催化剂(基于环境上的考虑)来制备2-金刚烷醇和2-金刚烷酮。
为了解决上述常规技术问题并在短时间内有效地选择性制备2-金刚烷醇和2-金刚烷酮(基于环境上的考虑),本发明的发明人在进行深入研究后发现,可以通过用路易斯酸或固体酸催化剂等催化剂,使1-金刚烷醇在所述催化剂与至少一种选自羧酸、磺酸和磷酸的酸共存时发生反应,从而解决了上述问题,也达到了上述目的。因此,根据上述发现完成了本发明。
因此,本发明提供:
(1)一种由1-金刚烷醇制备2-金刚烷醇和2-金刚烷酮的方法,其中使用包含至少一种选自路易斯酸和固体酸的酸催化剂的物质作催化剂,该酸催化剂与至少一种选自羧酸、磺酸和磷酸的酸共存;
(2)根据(1)所述的制备2-金刚烷醇和2-金刚烷酮的方法,其中所述固体酸是至少一种选自以下的物质:沸石、氧化锆、二氧化硅-氧化铝(silica-alumina)、氧化铝、杂多酸和阳离子交换树脂;
(3)根据(1)或(2)所述的制备2-金刚烷醇和2-金刚烷酮的方法,其中与所述酸催化剂共存的至少一种选自羧酸、磺酸和磷酸的酸的用量,对于1-金刚烷醇来说摩尔比为150以下;
(4)根据(1)-(3)中任一项所述的制备2-金刚烷醇和2-金刚烷酮的方法,其中反应温度范围为30-250℃;
(5)根据(1)-(4)中任一项所述的制备2-金刚烷醇和2-金刚烷酮的方法,其中与所述酸催化剂共存的酸是至少一种选自以下的酸:卤代羧酸、卤代磺酸和烷基磺酸。
实施本发明的最佳方式
[0006]
本发明详述如下。
就本发明的制备2-金刚烷醇和2-金刚烷酮的方法而言,在由1-金刚烷醇制备2-金刚烷醇和2-金刚烷酮的方法中,使用包含至少一种选自羧酸、磺酸和磷酸的酸并且与路易斯酸或固体酸共存的物质作为催化剂。
[0007]
在本发明中使用至少一种选自路易斯酸和固体酸的酸作为酸催化剂。
作为路易斯酸,例如可以列举出氯化铝、氯化铁、四氯化锡、四氯化钛、三氟化硼、三氟化硼络合物、三溴化硼、溴化铝、氯化稼、溴化稼等。
[0008]
使用至少一种选自以下的物质作为固体酸:沸石、氧化锆、二氧化硅-氧化铝、氧化铝、杂多酸和阳离子交换树脂。
作为沸石,可以列举出A型、L型、X型、Y型、ZSM-5等,优选使用H-形式的超稳定Y型沸石(HUSY),这种沸石是用硫酸处理的NH4-形式的Y型沸石。
另外,可以使用与盐酸、硫酸、磷酸、三氟化硼等进一步连接的氧化锆、二氧化硅-氧化铝、氧化铝等,例如硫酸化氧化锆。
杂多酸是具有多核结构的多元酸,其中两种以上的含氧酸进行缩合,而且使用磷、硅、砷和锗作为杂原子,使用钼、钨、铌、钒等作为多原子。具体地讲,可以列举出硅钨酸、硅钼酸等。
另外,阳离子交换树脂是具有可交换离子的不溶性多孔合成树脂,例如这样的聚合酸:其中酸性基团(例如酚式羟基、羧基、磺基等)与母体合成树脂(例如与二乙烯基苯交联的聚苯乙烯等)键合。
在上述酸催化剂中,优选使用上述固体酸,尤其更优选使用沸石和杂多酸。
[0009]
另外,与酸催化剂共存的至少一种选自羧酸、磺酸和磷酸的酸的添加量相对于1mol 1-金刚烷醇通常为例如150mol以下,优选1-100mol。通过设定至少一种选自羧酸、磺酸和磷酸的酸的添加量在上述范围内,可以使氧化反应速率增加。
作为上述羧酸,可以列举出一元羧酸(例如甲酸、乙酸、丙酸、丁酸等)、二元羧酸(例如乙二酸、丙二酸、丁二酸等)、芳族羧酸(例如苯甲酸、苯二甲酸等)、卤代羧酸(例如一氟乙酸、二氟乙酸、三氟乙酸、一氯乙酸、二氯乙酸、三氯乙酸等)。
另外,作为磺酸,可以列举出烷基磺酸(例如甲磺酸、乙磺酸等)、芳族磺酸例如苯磺酸、甲苯磺酸等)、卤代磺酸(例如三氟甲烷磺酸等)。
另外,作为磷酸,可以列举出正磷酸、偏磷酸(methaphosphoricacid)、焦磷酸、多磷酸等。
其中,优选卤代羧酸、卤代磺酸和烷基磺酸,尤其更优选卤代羧酸和卤代磺酸。
这些羧酸、磺酸和磷酸可单独使用或者两种以上合用。
[0010]
另外,反应温度范围通常优选为30-250℃,更优选范围为50-250℃。通过在如上所述的温度范围内进行反应,减少了因副反应导致的重馏分,并可阻止对2-金刚烷酮或2-金刚烷醇的选择性下降。
反应时间取决于反应温度、所用酸催化剂的量、共存的羧酸、磺酸和磷酸的种类和用量以及1-金刚烷醇的量等,通常无法具体化,但是在分批反应中,反应时间通常为0.5-20小时,优选1-10小时。
另外,在固定床流通式反应中,1-金刚烷醇的重时空速(WHSV)范围为0.001-50h-1,优选0.005-20h-1,其中优选进行氧化反应。
[0011]
作为用于本发明的氧化反应,通常使用以下方法进行反应:通过使用与酸催化剂共存且作为溶剂的羧酸、磺酸和磷酸,其中在酸催化剂的存在下,溶解给定量的l-金刚烷醇,然后升高反应温度。
作为溶剂,优选使用作为添加剂的上述羧酸、磺酸和磷酸,但是为了适当进行反应的目的,也可使用溶剂。然而,在此情况下,有必要选择溶解1-金刚烷醇并对酸催化剂稳定的溶剂。
对于这样的溶剂,可以列举出例如卤代烃化合物(例如二氯乙烷等)、具有惰性取代基的苯衍生物(例如硝基苯、氯苯等)。
[0012]
另外,对反应装置没有具体限制,只要能允许适当搅拌和加热即可,因为没有使用硫酸作为氧化剂,所以也无需使用昂贵的耐腐蚀材料。
氧化反应后,按照常规方法,从反应系统中分离出2-金刚烷酮和2-金刚烷醇。
实施例
[0013]
下面的实施例用于进一步说明本发明;然而,应当知道,本发明并不限于这些实施例。
根据内部标准方法,通过气相色谱,对原料和产物进行定量分析。
[0014]
实施例1
在100ml三颈烧瓶中,装有0.4g 1-金刚烷醇和20g一氯乙酸。搅拌所得混合物,将温度升至150℃。当温度达到150℃后,向混合物中加入5g硅钨酸(300℃干燥2小时),使反应进行2小时。反应完成后,过滤反应液,加入NaOH水溶液并冷却,直到所得溶液的pH为9。然后,溶液用20ml甲苯萃取。萃取液通过气相色谱分析。结果见表1。
[0015]
实施例2
反应、后处理和分析都按照与实施例1完全相同的方法进行,只是使用2g H-形式超稳定Y型沸石[(HUSY),300℃干燥3小时,其中二氧化硅-氧化铝比即SiO2/Al2O3=10]替代5g硅钨酸。结果见表1。
[0016]
实施例3
反应、后处理和分析都按照与实施例1完全相同的方法进行,只是使用三氯乙酸替代一氯乙酸。结果见表1。
[0017]
实施例4
反应、后处理和分析都按照与实施例1完全相同的方法进行,只是使用三氟乙酸替代一氯乙酸。结果见表1。
[0018]
实施例5
反应、后处理和分析都按照与实施例1完全相同的方法进行,只是使用乙酸替代一氯乙酸。结果见表1。
[0019]
实施例6
反应、后处理和分析都按照与实施例1完全相同的方法进行,只是使用甲烷磺酸替代一氯乙酸。结果见表1。
[0020]
比较实施例1
反应、后处理和分析都按照与实施例1完全相同的方法进行,只是加入20g正十四烷作为溶剂而不加入一氯乙酸,但是没有进行反应。
[0021]
比较实施例2
反应、后处理和分析都按照与实施例2完全相同的方法进行,只是加入20g正十四烷作为溶剂而不加入一氯乙酸,但是没有进行反应。
[0022]
比较实施例3
反应、后处理和分析都按照与实施例1完全相同的方法进行,只是不加入硅钨酸,但是没有进行反应。
[0023]
参考实施例1
反应、后处理和分析都按照与实施例1完全相同的方法进行,只是使用20g硫酸作为酸催化剂和添加剂。结果见表1。
[0024]
表1
添加剂 | 酸催化剂 | 2-金刚烷醇收率(mol%) | 2-金刚烷酮收率(mol%) | 反应时间(小时) | |
实施例1 | 一氯乙酸 | 硅钨酸 | 11 | 24 | 2 |
实施例2 | 一氯乙酸 | HUSY(Y型沸石) | 22 | 15 | 2 |
实施例3 | 一氯乙酸 | 硅钨酸 | 12 | 24 | 2 |
实施例4 | 乙酸 | 硅钨酸 | 4 | 13 | 2 |
实施例5 | 三氟乙酸 | 硅钨酸 | 11 | 23 | 2 |
实施例6 | 甲烷磺酸 | 硅钨酸 | 12 | 22 | 2 |
比较实施例1 | 无 | 硅钨酸 | 0 | 0 | 2 |
比较实施例2 | 无 | HUSY(Y型沸石) | 0 | 0 | 2 |
比较实施例3 | 一氯乙酸 | 无 | 0 | 0 | 2 |
参考实施例1 | 98%硫酸 | 0 | 2 | 2 |
工业实用性
[0025]
本发明是在短时间内高效制备2-金刚烷酮和2-金刚烷醇的方法,2-金刚烷酮和2-金刚烷醇可用于药用化学品、农用化学品、半导体、磁记录媒体、光学材料、耐热塑料、功能性材料(例如涂料和胶粘剂等)、化妆品、润滑油等领域。
Claims (5)
1.一种由1-金刚烷醇制备2-金刚烷醇和2-金刚烷酮的方法,其中使用包含至少一种选自路易斯酸和固体酸的酸催化剂的物质作为催化剂,该酸催化剂与至少一种选自羧酸、磺酸和磷酸的酸共存。
2.权利要求1的制备2-金刚烷醇和2-金刚烷酮的方法,其中所述固体酸是至少一种选自以下的物质:沸石、氧化锆、二氧化硅-氧化铝、氧化铝、杂多酸和阳离子交换树脂。
3.权利要求1或2的制备2-金刚烷醇和2-金刚烷酮的方法,其中与所述酸催化剂共存的至少一种选自羧酸、磺酸和磷酸的酸的量,对于1-金刚烷醇来说摩尔比为150以下。
4.权利要求1-3中任一项的制备2-金刚烷醇和2-金刚烷酮的方法,其中反应温度范围为30-250℃。
5.权利要求1-4中任一项的制备2-金刚烷醇和2-金刚烷酮的方法,其中与所述酸催化剂共存的酸是至少一种选自以下的酸:卤代羧酸、卤代磺酸和烷基磺酸。
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