CN1107044C - 2－环十二碳烷基－1－丙醇的制备方法 - Google Patents
2－环十二碳烷基－1－丙醇的制备方法 Download PDFInfo
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- CN1107044C CN1107044C CN98806314A CN98806314A CN1107044C CN 1107044 C CN1107044 C CN 1107044C CN 98806314 A CN98806314 A CN 98806314A CN 98806314 A CN98806314 A CN 98806314A CN 1107044 C CN1107044 C CN 1107044C
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- Prior art keywords
- peroxide
- propionic acid
- ester
- hydrogenation
- hydrogen
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- WKHTUDYDJUHYMK-UHFFFAOYSA-N 2-cyclododecylpropan-1-ol Chemical compound OCC(C)C1CCCCCCCCCCC1 WKHTUDYDJUHYMK-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 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 claims abstract description 20
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 35
- 238000005984 hydrogenation reaction Methods 0.000 claims description 30
- -1 triacontanol ester Chemical class 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052702 rhenium Inorganic materials 0.000 claims description 8
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012933 diacyl peroxide Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 150000004965 peroxy acids Chemical class 0.000 claims description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 3
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 claims 1
- IAYHEAJJFYJHJI-UHFFFAOYSA-N 2-cyclododecylpropanoic acid Chemical compound OC(=O)C(C)C1CCCCCCCCCCC1 IAYHEAJJFYJHJI-UHFFFAOYSA-N 0.000 abstract 2
- 241000402754 Erythranthe moschata Species 0.000 abstract 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 abstract 1
- 150000005599 propionic acid derivatives Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001925 cycloalkenes Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229940017219 methyl propionate Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000008786 sensory perception of smell Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 241000972155 Moschus Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 238000006680 Reformatsky reaction Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical class CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- VHFCHIFMOIOXSV-UHFFFAOYSA-L [Cu].[Ba].[Cr](=O)(O)O Chemical compound [Cu].[Ba].[Cr](=O)(O)O VHFCHIFMOIOXSV-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/13—Monohydroxylic alcohols containing saturated rings
- C07C31/133—Monohydroxylic alcohols containing saturated rings monocyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
本发明涉及通过环十二碳烯和过量丙酸或丙酸衍生物在催化剂量的自由基引发剂存在下反应并随后将生成的2-环十二碳烷基丙酸或相应的2-环十二碳烷基丙酸衍生物催化氢化在工业上制备寻找的散发麝香树根气味的物质2-环十二烷基丙醇的有益方法。
Description
本申请涉及用于从环十二碳烯和丙酸或其衍生物制备2-环十二烷基-1-丙醇的有益的工业方法。
2-环十二烷基-1-丙醇(也称为羟基龙涎香烷)可发出麝香类的气味并越来越重要(参考EP278384B1)。其现有的制备方法是从环十二碳酮和2-溴丙酸烷基酯开始(参考例如Angew.Chem.108(1996)，1312-13或EP278384)。在该方法中，在与锌的雷福尔马茨基反应中形成不饱和的2-环十二碳烷基丙酸酯。生成的溴化锌不得不进行处理。生成的酯随后被催化氢化，或如EP278384所公开的用氢化铝锂还原。通过有机卤化合物形成的化合物一般还含有痕量的卤素。由于氢化形成的卤化氢，应预期到在酯催化氢化生成相应醇的过程中反应器材料和氢化催化剂的严重腐蚀。另外，已知痕量卤素小到约1ppm也会有干扰。
上述方法特别适合用于制备少量的2-环十二碳烷基-1-丙醇。但是该方法不适用于工业生产，即，以数吨的规模制备2-环十二碳烷基-丙醇，原因如下：
1.作为起始化合物使用的2-溴丙酸烷基酯和可从其获得的α-溴-锌丙酸烷基酯特别昂贵。
2.通过氢化环十二碳三烯并随后氧化生成的环十二碳烷制备环十二碳酮在工业上非常复杂，因此也非常昂贵。
3.如上文所述，在氢化中形成的卤化氢对反应器和氢化催化剂有腐蚀，这需要使用非常昂贵的反应器材料，并导致氢化催化剂的使用寿命缩短。
4.在反应中生成的溴化锌导致了大量废水问题，需要复杂的后处理或处置方法。
5.如EP278384所述的使用氢化铝锂的还原在工业合成中是禁止的。
本发明的目的是开发一种工业制备2-环十二碳烷基丙醇的方法，其避免了现有方法的缺点。该新方法因此应从尽可能易于获得并因此便宜的原料开始，并应在最少的易于工业实现的反应步骤中以好的产率得到嗅觉愉悦的产品，同时没有由于大量盐的生成而导致的废水问题。
我们已经发现，使环十二碳烯与过量的丙酸或丙酸的衍生物在催化量的自由基引发剂存在下反应，在氢化催化剂上用氢气催化氢化生成的2-环十二碳烷基丙酸或相应的2-环十二碳烷基丙酸衍生物，即使在工业规模上也可以制备2-环十二碳烷基-1-丙醇，通过该方法可达到上述目的。
令人惊奇的是，用这种方法可容易地以工业规模合成需要的羟基龙涎香烷并达到嗅觉上令人满意的纯度，该方法从环十二碳烯开始，仅包括两个反应步骤，通过丁二烯三聚并随后部分氢化可容易地制备环十二碳烯。
尽管《合成》(Synthesis)(1970)No.3，99-140已经公开了在自由基引发剂存在下可将羧酸或羧酸衍生物与烯烃加成，与许多开链烯烃反应的高产率相比，根据loc.cit得到的环烯烃的反应产率，环戊烯和环己烯分别仅有理论量的17％和10％，因此绝对不能预见到基于与环十二碳烯的反应的工业生产可以获得令人满意的产率。
《有机化学方法》(Methoden der organischen Chemie)(Houben-Wely)，卷V/1b，第4版，1997，第1058-1063页已经公开了羧酸或羧酸衍生物与烯烃的自由基加成。但是，并没有提及丙酸或其衍生物与作为烯烃的环十二碳烯的加成。由于在自由基引发剂引发的反应中通常生成相对大量不需要的副产物，因此更不能预见到用这类反应可制备出嗅觉上足够纯的羟基龙涎香烷。
本发明因此涉及一种制备2-环十二碳烷基丙醇的方法，包括
A.在催化量的自由基引发剂存在下将环十二碳烯与丙酸或其一种衍生物反应，和
B.将形成的2-环十二碳烷基丙酸或其相应的衍生物与氢气在适当的氢化催化剂上在100-300℃和20-350巴进行反应。
当所用的丙酸衍生物是其与低级(C1-C6)链烷醇的酯时，该新方法是特别有利的。
当自由基引发剂是过氧化氢、过硼酸盐、过重硫酸盐、过一硫酸盐、过酸、氢过氧化物、二烷基过氧化物、过酯、二酰基过氧化物、过碳酸氢盐、过缩酮或酮过氧化物，特别是易于获得的二叔丁基过氧化物时，该新方法特别有利。
当使用的氢化催化剂含有一种或多种元素周期表Ib、VIb、VIIb和VIIIb和IIIa、IVa和Va族的元素时，特别是当使用的氢化催化剂含有铜、钴或铼的至少一种元素时，可良好地进行第二反应步骤，即催化氢化。
通过将丁二烯三聚成环十二碳三烯(参考Angew.Chem.75(1963)10)并随后将其部分氢化可容易地制备作为起始化合物使用的环十二碳烯。因此无需已知制备方法中的完全氢化并随后将生成的环十二碳烷氧化成环十二碳酮。
通过一般已知的方法可产生羧酸或其衍生物加成所需的自由基。可述及的例子为诸如过氧化物之类的自由基引发剂的辐射和分解。优选过氧化物的分解。可述及的过氧化物的例子是过氧化氢、过硼酸、过重硫酸盐、过一硫酸盐、过酸、氢过氧化物、二烷基过氧化物、过酯、二酰基过氧化物、过碳酸氢盐、过缩酮或酮过氧化物。热引发这些自由基引发剂的分解是有利的。以催化量使用过氧化合物。因此，根据本发明每摩尔环烯烃使用的过氧化物的量一般为0.01-1摩尔当量，优选0.05-0.8摩尔当量，特别是0.1-0.6摩尔当量。自由基加成采用的温度取决于使用的过氧化合物。由于每种过氧化合物在不同的温度开始分解，该新方法的温度范围非常大。一般为30-250℃。例如，如果使用二叔丁基过氧化物，温度优选为120-160℃。
反应通常在反应物呈液态的压力下进行，对于压力没有上限。
丙酸或其衍生物对环十二碳烯的摩尔比一般在400和1之间，优选150和1之间，特别是100和1之间。另外，丙酸或其衍生物起溶剂的作用是有利的。
对于新方法特别适合的丙酸衍生物是其酯。可述及的特别适合的酯是甲酯、乙酯、丙酯、正丁酯、异丁酯、叔丁酯、叔戊酯、正庚酯和正己酯。但是，还可使用酰胺或丙酸酐。
反应可分批、半连续或连续进行。
反应的排出物可在第二步氢化前处理，但也可以直接在下一步使用。处理一般限制在除去过量的丙酸或过量的丙酸衍生物和未反应的环烯烃。所述低沸物优选通过蒸馏除去。它们可返回到工艺的第一步。
如果希望得到纯的2-环十二碳烷基丙酸，可对除去丙酸后的残留物本身进行蒸馏，或通过结晶得到纯净形式的酸。2-环十二碳烷基丙酸的氢化或其衍生物的氢化可在气相或液相使用来自工艺的第一步的粗排出物、除去丙酸或丙酸衍生物的粗排出物或纯净物进行。
该新方法中通常使用的氢化催化剂是多相的催化剂，单也可以使用适合氢化羰基的均相的催化剂。它们可作为固定床催化剂排列，或以流动形式使用，例如在流化床反应器中。在例如Houben-Weyl的有机化学方法(Methoden der Organischen Chemie)卷IV/1c，第16-26页描述了用于该目的的氢化催化剂。
其中优选的氢化催化剂是含有一种或多种元素周期表Ib、VIb、VIIb和VIIIb和IIIa、IVa和Va族的元素的，特别是含有铜、铬、铼、钴、铑、镍、钯、铁、铂、铟、锡和锑的那些。
在该新方法中使用的催化剂可以是例如沉淀的催化剂。这类催化剂可通过将它们的催化活性成分从其盐溶液中沉淀来制备，特别是从它们的硝酸盐和/或醋酸盐通过例如加入碱金属和/或碱土金属氢氧化物和/或碱金属和/或碱土金属碳酸盐溶液将它们以其微溶的氢氧化物、氧化物水合物、碱性盐或碳酸盐形式沉淀，然后干燥生成的沉淀，随后在一般300-700℃、特别是400-600℃煅烧，转化成相应的氧化物、混合的氧化物和/或混合的多化合价的氧化物，通过用氢气或含氢气的气体在一般50-700℃、特别是100-400℃处理将其还原，从而转化成实际的催化活性形式，得到相关的金属和/或低氧化态的氧化物。一般继续该还原，直到不再生成水。为了制备含有载体材料的沉淀催化剂，可在相关的载体材料存在下沉淀催化活性成分。但是，从相关的盐溶液将催化活性成分与载体材料同时沉淀也是有利的。在该新方法中优选使用的氢化催化剂是含有沉积在载体材料上催化氢化反应的金属或金属化合物的那些催化剂。适用于新方法所用催化剂的载体材料一般是那些其中例如通过浸渗已经将催化氢化的成分施加到载体材料上的那些。
将催化活性金属施加到载体上的方法一般不特别地限定，可采用各种方法。例如用相关元素的盐或氧化物的溶液或悬浮液浸渗这些载体材料，干燥并随后通过使用还原剂、优选用氢气或复合氢化物还原金属化合物，得到相关金属或化合物的较低氧化态，可以将催化活性金属施加到这些载体材料中。另一种将催化活性金属施加到这些载体的可能性包括用易于进行热分解的盐例如硝酸盐或易于进行热分解的配合化合物例如催化活性金属的羰基或氢化物配合物的溶液浸渗载体，将如此浸渗过的载体在300-600℃加热以热分解吸附的金属化合物。该热分解优选在保护气气氛中进行。适合的保护气的例子是氮气、二氧化碳、氢气或惰性气体。催化活性金属可通过蒸气沉积或火焰喷射进一步沉积在催化剂载体上。在这些承载的催化剂中催化活性金属的含量对于成功进行新方法原则上并不是重要的。在这些承载的催化剂中催化活性金属的含量越高，与较低含量相比，越能获得更高的空时转化，这对于技术人员是不言自明的。基于整个催化剂，一般使用的承载的催化剂含有0.1-90％重量、优选0.5-40％重量催化活性金属。由于这些含量数值涉及包括载体材料的整个催化剂，但是不同的载体材料具有非常不同的比重和比表面积，所以数值比这些值低或高也有可能，只要对于新方法的结果没有不利影响。当然也可能将多种催化活性金属施加到特定的载体材料上。另外，可用例如DE-A-2519817、EP-A147219和EP-A285420的方法将催化活性金属施加到载体上。催化活性金属作为合金存在于上述公开文献中所述的催化剂中，这些合金通过对例如用上述金属的盐或配合物浸渗进行热处理和/或还原制备。
沉淀的催化剂和承载的催化剂的活化还可在反应开始时就地通过存在的氢气进行，但是这些催化剂优选在使用前独立地活化。
一般可使用的载体材料是铝和钛的氧化物、二氧化锆、二氧化硅、诸如蒙脱石的粘土、诸如硅酸镁或硅酸铝的硅酸盐、诸如ZSM-5或ZSM-10沸石的沸石或活性炭。优选的载体材料是氧化铝、二氧化钛、二氧化硅、二氧化锆和活性炭。当然也可以使用各种载体材料的混合物作为可用于新方法的催化剂的载体。
可用于新方法的多相催化剂的例子如下：
活性炭上的钴、二氧化硅上的钴、氧化铝上的钴、活性炭上的铼、二氧化硅上的铼、活性炭上的铼/锡、活性炭上的铼/铂、活性炭上的铜、铜/二氧化硅、铜/氧化铝、亚铬酸铜、亚铬酸钡铜、铜/氧化铝/氧化镁、铜/氧化铝/氧化锌和在DE-A3932332、US-A3449445、EP-A 44 444、EP-A 147 219、DE-A 3 904 083、DE-A 2 321 101、EP-A 415 202、DE-A 2 366 264、EP 0 552 463和EP-A 100 406中公开的催化剂。
特别优选的催化剂含有金属铜、钴或铼中的至少一种。
连续进行新方法是有利的。为此例如可使用管式反应器，其中催化剂以固定床的形式排列是有利的，或使用流化床反应器，其中催化剂被气流搅动。
氢化可使用或不使用溶剂。如果使用溶剂，可以是水或醇，诸如甲醇或乙醇。醚也适用，诸如四氢呋喃、二噁烷或乙二醇二甲醚，还有烃类，诸如己烷或环己烷。
在100-300℃、优选150-260℃进行氢化。如果在气相进行氢化，压力为20-80巴。如果在液相进行，压力在50-350巴，优选100-320巴，特别是130-300巴。
下列实施例用于具体说明新方法，但不构成任何限定。
实施例1
370g(5mol)丙酸在反应容器中加热到140℃。然后在5小时期间滴加84g(0.5mol)环十二碳烯和14.6g(0.1mol)二叔丁基过氧化物的混合物。然后再进行2小时回流。反应混合物冷却后，在30毫巴将过量的丙酸和生成的叔丁醇蒸出。降低压力，然后蒸出未反应的环十二碳烯，得到31g残留物。
将得到的残留物溶于280ml乙醇中，在高压釜中在220℃和220巴用氢气在已经用氢气在180℃活化的31g铜催化剂上进行间歇氢化，铜催化剂的未活化形式具有下列组成：70％质量CuO、25％质量ZnO和5％质量Al2O3。然后将混合物冷却并减压。气相色谱分析(GC)表明扣除乙醇排出物含有57.7％2-环十二碳烷基-1-丙醇和14％2-环十二烷基丙酸乙酯，剩余物主要是高沸产物。基于转化率64％的反应的环十二碳烯，所需羟基龙涎香烷的产率约为理论量的60％。
实施例2
880g(10mol)丙酸甲酯、163g(0.94mol)96％重量的环十二碳烯和26g(0.18mol))二叔丁基过氧化物在高压釜中在140℃和5.1巴的自生压力搅拌反应20小时。
气相色谱分析(GC)表明反应排出物含有98g环十二碳烯和50g2-环十二烷基丙酸甲酯。这相应于52％的选择性和60％的转化率。
蒸馏后，2-环十二烷基丙酸甲酯的沸点为112℃/3毫巴。
实施例3
将500g实施例1中由丙酸和环十二碳烯加成反应得到的残留物溶于500g正丁醇中，在如实施例1制备的25ml钴催化剂上按照DE2321101以下流式工艺在管式反应器中连续氢化(进料约20g/小时，220巴，220-230℃)。为了完全转化，在相同条件下对氢化排出物再进行氢化。
除了溶剂正丁醇，排出物含有约70％2-环十二碳烷基丙醇。其它成分主要是环十二碳烷二聚物和低聚物。氢化排出物除去丁醇后在1米高的填料塔中在1毫巴进行分馏。塔底温度185℃，得到总量260g的2-环十二碳烷基丙醇，纯度为97-99.8％，沸点123-132℃。得到的所有馏分具有质量令人满意的香味。
Claims (7)
1.一种制备2-环十二碳烷基-1-丙醇的方法，包括
A.在催化量的自由基引发剂存在下将环十二碳烯与丙酸或其一种衍生物反应，和
B.将形成的2-环十二碳烷基丙酸或其相应的衍生物与氢气在适当的氢化催化剂上在100-300℃和20-350巴进行反应。
2. 根据权利要求1的方法，其中使用的丙酸衍生物是其C1-C6链烷醇酯。
3.根据权利要求1的方法，其中使用的自由基引发剂是过氧化氢、过硼酸盐、过重硫酸盐、过一硫酸盐、过酸、氢过氧化物、二烷基过氧化物、过酯、二酰基过氧化物、过碳酸氢盐、过缩酮或酮过氧化物。
4.根据权利要求3的方法，其中使用二叔丁基过氧化物作为自由基引发剂。
5.根据权利要求1的方法，其中使用的氢化催化剂含有一种或多种元素周期表Ib、VIb、VIIb和VIIIb和IIIa、IVa和Va族的元素。
6.根据权利要求1的方法，其中使用的催化剂含有铜、钴或铼中至少一种元素。
7.根据权利要求1的方法，其中使用丙酸酐作为丙酸衍生物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19725533.7 | 1997-06-17 | ||
| DE19725533A DE19725533A1 (de) | 1997-06-17 | 1997-06-17 | Verfahren zur Herstellung von 2-Cyclododecyl-1-propanol |
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| Publication Number | Publication Date |
|---|---|
| CN1260773A CN1260773A (zh) | 2000-07-19 |
| CN1107044C true CN1107044C (zh) | 2003-04-30 |
Family
ID=7832703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98806314A Expired - Fee Related CN1107044C (zh) | 1997-06-17 | 1998-06-04 | 2－环十二碳烷基－1－丙醇的制备方法 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6303836B1 (zh) |
| EP (1) | EP0993427B1 (zh) |
| JP (1) | JP2002504129A (zh) |
| KR (1) | KR20010013841A (zh) |
| CN (1) | CN1107044C (zh) |
| AU (1) | AU8212898A (zh) |
| BR (1) | BR9810438A (zh) |
| CA (1) | CA2290780A1 (zh) |
| DE (2) | DE19725533A1 (zh) |
| ES (1) | ES2182335T3 (zh) |
| IL (1) | IL132968A0 (zh) |
| WO (1) | WO1998057914A1 (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0926121A1 (en) * | 1997-10-28 | 1999-06-30 | Quest International B.V. | Reaction of alkenes with epoxides, the products thereof and their use as fragrance compounds |
| DE10023256A1 (de) | 2000-05-12 | 2001-11-15 | Basf Ag | (+)-und(-)-2-Cyclododecylpropanol und (+)-und(-)-2-Cyclododecylpropionsäure sowie deren Herstellung und Verwendung |
| DE10229474A1 (de) * | 2002-07-01 | 2004-01-15 | Symrise Gmbh & Co. Kg | Neue Riechstoffe und Verfahren zu ihrer Herstellung |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2357514A1 (fr) * | 1976-07-09 | 1978-02-03 | Basf Ag | Nouvelles substances odorantes a odeur de musc et procede pour leur preparation |
| EP0278384A2 (de) * | 1987-02-06 | 1988-08-17 | Consortium für elektrochemische Industrie GmbH | Alkohole und Ether mit Cyclododecyl- und Cyclododecenylgruppen, deren Herstellung und Verwendung als Duftstoffe |
-
1997
- 1997-06-17 DE DE19725533A patent/DE19725533A1/de not_active Withdrawn
-
1998
- 1998-06-04 ES ES98932116T patent/ES2182335T3/es not_active Expired - Lifetime
- 1998-06-04 DE DE59805432T patent/DE59805432D1/de not_active Expired - Lifetime
- 1998-06-04 AU AU82128/98A patent/AU8212898A/en not_active Abandoned
- 1998-06-04 JP JP50366299A patent/JP2002504129A/ja active Pending
- 1998-06-04 KR KR1019997011862A patent/KR20010013841A/ko not_active Application Discontinuation
- 1998-06-04 US US09/424,258 patent/US6303836B1/en not_active Expired - Fee Related
- 1998-06-04 IL IL13296898A patent/IL132968A0/xx unknown
- 1998-06-04 EP EP98932116A patent/EP0993427B1/de not_active Expired - Lifetime
- 1998-06-04 WO PCT/EP1998/003339 patent/WO1998057914A1/de not_active Application Discontinuation
- 1998-06-04 CA CA002290780A patent/CA2290780A1/en not_active Abandoned
- 1998-06-04 BR BR9810438-1A patent/BR9810438A/pt not_active IP Right Cessation
- 1998-06-04 CN CN98806314A patent/CN1107044C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2357514A1 (fr) * | 1976-07-09 | 1978-02-03 | Basf Ag | Nouvelles substances odorantes a odeur de musc et procede pour leur preparation |
| EP0278384A2 (de) * | 1987-02-06 | 1988-08-17 | Consortium für elektrochemische Industrie GmbH | Alkohole und Ether mit Cyclododecyl- und Cyclododecenylgruppen, deren Herstellung und Verwendung als Duftstoffe |
Also Published As
| Publication number | Publication date |
|---|---|
| IL132968A0 (en) | 2001-03-19 |
| WO1998057914A1 (de) | 1998-12-23 |
| ES2182335T3 (es) | 2003-03-01 |
| DE19725533A1 (de) | 1998-12-24 |
| EP0993427A1 (de) | 2000-04-19 |
| JP2002504129A (ja) | 2002-02-05 |
| CN1260773A (zh) | 2000-07-19 |
| EP0993427B1 (de) | 2002-09-04 |
| BR9810438A (pt) | 2000-09-19 |
| DE59805432D1 (de) | 2002-10-10 |
| CA2290780A1 (en) | 1998-12-23 |
| AU8212898A (en) | 1999-01-04 |
| US6303836B1 (en) | 2001-10-16 |
| KR20010013841A (ko) | 2001-02-26 |
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