EP2925712A1 - Procédé de production d'alcanols tertiaires cyclohexyl-substitués - Google Patents
Procédé de production d'alcanols tertiaires cyclohexyl-substituésInfo
- Publication number
- EP2925712A1 EP2925712A1 EP13802553.1A EP13802553A EP2925712A1 EP 2925712 A1 EP2925712 A1 EP 2925712A1 EP 13802553 A EP13802553 A EP 13802553A EP 2925712 A1 EP2925712 A1 EP 2925712A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- compound
- cycloalkyl
- alkyl
- reaction
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 130
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000003205 fragrance Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims description 98
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 21
- 229910052707 ruthenium Inorganic materials 0.000 claims description 21
- 125000006272 (C3-C7) cycloalkyl group Chemical group 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052703 rhodium Inorganic materials 0.000 claims description 13
- 239000010948 rhodium Substances 0.000 claims description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002537 cosmetic Substances 0.000 claims description 11
- 239000003599 detergent Substances 0.000 claims description 11
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000004753 textile Substances 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 32
- 239000000463 material Substances 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 150000002739 metals Chemical class 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 15
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 14
- -1 1-methylpentyl Chemical group 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- MAJYELQKOLTSPZ-UHFFFAOYSA-N 1-cyclohexyl-3-methylpentan-3-ol Chemical compound CCC(C)(O)CCC1CCCCC1 MAJYELQKOLTSPZ-UHFFFAOYSA-N 0.000 description 8
- 239000012876 carrier material Substances 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- 239000000499 gel Substances 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methyl-2-butanol Substances CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 5
- AEJRTNBCFUOSEM-UHFFFAOYSA-N 3-Methyl-1-phenyl-3-pentanol Chemical compound CCC(C)(O)CCC1=CC=CC=C1 AEJRTNBCFUOSEM-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- KZZASWGRLOTITL-UHFFFAOYSA-N 4-cyclohexyl-2-methylbutan-2-ol Chemical compound CC(C)(O)CCC1CCCCC1 KZZASWGRLOTITL-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QHLDMOSAIDDEPM-UHFFFAOYSA-N 1-cyclohexyl-3,4,4-trimethylheptan-3-ol Chemical compound CCCC(C)(C)C(C)(O)CCC1CCCCC1 QHLDMOSAIDDEPM-UHFFFAOYSA-N 0.000 description 3
- ZMABXRQEKCEGPP-UHFFFAOYSA-N 1-cyclohexyl-3,4-dimethyloctan-3-ol Chemical compound CCCCC(C)C(C)(O)CCC1CCCCC1 ZMABXRQEKCEGPP-UHFFFAOYSA-N 0.000 description 3
- VSRCYGOKEUNQIA-UHFFFAOYSA-N 1-cyclohexyl-3,5,5-trimethylheptan-3-ol Chemical compound CCC(C)(C)CC(C)(O)CCC1CCCCC1 VSRCYGOKEUNQIA-UHFFFAOYSA-N 0.000 description 3
- OEYLSIWDBBLXEW-UHFFFAOYSA-N 1-cyclohexyl-3,5-dimethylheptan-3-ol Chemical compound CCC(C)CC(C)(O)CCC1CCCCC1 OEYLSIWDBBLXEW-UHFFFAOYSA-N 0.000 description 3
- XHIVDEMLPRTAOL-UHFFFAOYSA-N 1-cyclohexyl-3,5-dimethyloctan-3-ol Chemical compound CCCC(C)CC(C)(O)CCC1CCCCC1 XHIVDEMLPRTAOL-UHFFFAOYSA-N 0.000 description 3
- YQCJXRISMHWNLQ-UHFFFAOYSA-N 1-cyclohexyl-3,6,6-trimethylheptan-3-ol Chemical compound CC(C)(C)CCC(C)(O)CCC1CCCCC1 YQCJXRISMHWNLQ-UHFFFAOYSA-N 0.000 description 3
- SXJPVAYEQDJERL-UHFFFAOYSA-N 1-cyclohexyl-3,6-dimethyloctan-3-ol Chemical compound CCC(C)CCC(C)(O)CCC1CCCCC1 SXJPVAYEQDJERL-UHFFFAOYSA-N 0.000 description 3
- ZCEDURRLZWSYPO-UHFFFAOYSA-N 1-cyclohexyl-3,7-dimethyloctan-3-ol Chemical compound CC(C)CCCC(C)(O)CCC1CCCCC1 ZCEDURRLZWSYPO-UHFFFAOYSA-N 0.000 description 3
- KSTJUDSCAZRQHR-UHFFFAOYSA-N 1-cyclohexyl-3-ethylheptan-3-ol Chemical compound CCCCC(O)(CC)CCC1CCCCC1 KSTJUDSCAZRQHR-UHFFFAOYSA-N 0.000 description 3
- HKARUBXOYBIDJL-UHFFFAOYSA-N 1-cyclohexyl-3-ethylhexan-3-ol Chemical compound CCCC(O)(CC)CCC1CCCCC1 HKARUBXOYBIDJL-UHFFFAOYSA-N 0.000 description 3
- IAFOJTCRZQZOLX-UHFFFAOYSA-N 1-cyclohexyl-3-ethylnonan-3-ol Chemical compound CCCCCCC(O)(CC)CCC1CCCCC1 IAFOJTCRZQZOLX-UHFFFAOYSA-N 0.000 description 3
- KQVGOZRKKWHVLN-UHFFFAOYSA-N 1-cyclohexyl-3-ethyloctan-3-ol Chemical compound CCCCCC(O)(CC)CCC1CCCCC1 KQVGOZRKKWHVLN-UHFFFAOYSA-N 0.000 description 3
- KTUCUCNZDBSPFO-UHFFFAOYSA-N 1-cyclohexyl-3-methylheptan-3-ol Chemical compound CCCCC(C)(O)CCC1CCCCC1 KTUCUCNZDBSPFO-UHFFFAOYSA-N 0.000 description 3
- PUENDOHAAACRQS-UHFFFAOYSA-N 1-cyclohexyl-3-methylnonan-3-ol Chemical compound CCCCCCC(C)(O)CCC1CCCCC1 PUENDOHAAACRQS-UHFFFAOYSA-N 0.000 description 3
- CLKWSLIVIRHQPJ-UHFFFAOYSA-N 1-cyclohexyl-3-methyloctan-3-ol Chemical compound CCCCCC(C)(O)CCC1CCCCC1 CLKWSLIVIRHQPJ-UHFFFAOYSA-N 0.000 description 3
- BUJKXNZDTLNSKI-UHFFFAOYSA-N 1-cyclohexyl-4-cyclopentyl-3-methylpentan-3-ol Chemical compound C1CCCCC1CCC(C)(O)C(C)C1CCCC1 BUJKXNZDTLNSKI-UHFFFAOYSA-N 0.000 description 3
- OVCOIURLSIHPJD-UHFFFAOYSA-N 1-cyclohexyl-5-ethyl-3-methylheptan-3-ol Chemical compound CCC(CC)CC(C)(O)CCC1CCCCC1 OVCOIURLSIHPJD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000195940 Bryophyta Species 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 235000011929 mousse Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- UNSCMWYKJMSGIP-UHFFFAOYSA-N 1-cyclohexyl-3-methylhexan-3-ol Chemical compound CCCC(C)(O)CCC1CCCCC1 UNSCMWYKJMSGIP-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NIOYEYDJTAEDFH-UHFFFAOYSA-N 1-(2-hydroxyethoxy)-2-methylpropan-2-ol Chemical compound CC(C)(O)COCCO NIOYEYDJTAEDFH-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- DLHQZZUEERVIGQ-UHFFFAOYSA-N 3,7-dimethyl-3-octanol Chemical compound CCC(C)(O)CCCC(C)C DLHQZZUEERVIGQ-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 244000068485 Convallaria majalis Species 0.000 description 1
- 235000009046 Convallaria majalis Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 238000006229 Nazarov cyclization reaction Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010568 chiral column chromatography Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000002951 depilatory effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003051 hair bleaching agent Substances 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002884 skin cream Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
- C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
-
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
-
- 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
- C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
-
- 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
- C07C31/135—Monohydroxylic alcohols containing saturated rings monocyclic with a five or six-membered rings; Naphthenic alcohols
- C07C31/1355—Monohydroxylic alcohols containing saturated rings monocyclic with a five or six-membered rings; Naphthenic alcohols with a six-membered ring
Definitions
- the present invention relates to a process for the preparation of cyclohexyl-substituted tertiary alkanols, and to the use of such compounds as perfume.
- Fragrances are used in a variety of technical products and household products to cover unwanted odors or for olfactory improvement. Floral notes are of great interest, especially when used in detergents and cleaners. It is important for such uses that the fragrances not only have a pleasant odor, but also remain chemically stable over a longer period of time and can be incorporated into the corresponding product in a technically good manner. It is also desirable to have the lowest possible production process for the fragrances.
- 4-Cyclohexyl-2-methyl-2-butanol is a fragrance with lily-of-the-valley fragrance, the use of which as a component of fragrance compositions was first described in US 4,701,278.
- Preparation methods for 4-cyclohexyl-2-methyl-2-butanol have been described by Okazawa et al. (Can J. Chem., 60 (1982), 2180-93) and Ebel et al. (WO 201 1/1 17360) described.
- R and R 2 are independent selected from among groups of the formula (C 3-7 -cycloalkyl) x - (C 1-7 -alkyl) y , where either x and y are each 1 or one of the variables x and y is 1 and the other is 0.
- R 1 and R 2 are independently selected from C 1-7 -alkyl, C 3-7 -cycloalkyl and C 4-7 -cycloalkylalkyl.
- R 1 and R 2 together comprise a total of 3 to 1 1 carbon atoms, in particular 3 to 8 carbon atoms, preferably 3 to 5 carbon atoms and more preferably 3 carbon atoms.
- Ci-7-alkyl is a linear or branched alkyl radical having 1 to 7 carbon atoms.
- linear C 1-7 -alkyl are methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl
- branched C 1-7 -alkyl are isopropyl, sec-butyl, tert-butyl, iso- Hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl and 2-ethylbutyl.
- C3-7 cycloalkyl is a cycloalkyl radical of from 3 to 7 carbon atoms in total, which is bonded through one of the carbon ring atoms.
- This Cycloalkyl radical is unsubstituted or substituted with 1, 2 or 3 Ci-7-alkyl radicals as defined above, with the proviso that the cycloalkyl radical in total (ie including any alkyl substituents) comprises not more than 7 carbon atoms.
- Examples of an unsubstituted C 3-7 cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
- C4-7 cycloalkylalkyl is a linear or branched alkyl radical substituted with a cycloalkyl group and comprising 4 to 7 carbon atoms in total (i.e., including the cycloalkyl substituent).
- Examples of C4-7 cycloalkylalkyl are cyclohexylmethyl, cyclopentylmethyl and 1-cyclopentylethyl.
- R 1 and R 2 are independently selected from C 1-7 -alkyl and C 3-7 -cycloalkyl.
- the respective compounds within a particular of the described reaction pathways (hereinafter also referred to as "corresponding compounds") carry the same R 1 and R 2 .
- a preferred embodiment of the invention relates to a process for preparing 1-cyclohexyl-3-methyl-3-pentanol, comprising:
- the compound of the formula (Ia) is selected from 1-cyclohexyl-3-methyl-3-hexanol, 1-cyclohexyl-3-methyl-3-heptanol, 1-cyclohexyl-3-methyl-3- octanol, 1-cyclohexyl-3-methyl-3-nonanol, 1-cyclohexyl-3,4-dimethyl-3-octanol, 1-cyclohexyl-3,5-dimethyl-3-octanol, 1-cyclohexyl-3,6- dimethyl-3-octanol, 1-cyclohexyl-3,7-dimethyl-3-octanol, 1-cyclohexyl-3,4,4-trimethyl-3-heptanol, 1-cyclohexyl-3,5,5-trimethyl-3- heptanol, 1-cyclohexyl-3,6,6-trimethyl-3-heptanol
- the invention thus relates to a process for preparing a compound of the formula (Ia) with the steps described here and below and in the claims.
- the method has a number of advantages. It allows a highly atom economical production of a compound of formula (Ia) from very inexpensive basic chemicals, does not require any elaborate work-up steps and is therefore relatively inexpensive. The use of expensive and dangerous reagents such as methyllithium is not required.
- step a) and step b) can be carried out easily on an industrial scale and provide the respective products with high selectivity and good yields.
- step a) of the process according to the invention a secondary alkanol of the formula (II) is reacted with styrene.
- a corresponding phenyl-substituted tertiary alkanol of the formula (IIIa) forms as well as by-products, inter alia, toluene and ethylbenzene, which, however, can be separated off from the target product, for example by distillation.
- step a) in addition to the compound of the formula (IIIa), the corresponding (ie the same R 1 , R 2 ) methyl-substituted alkanol of the formula (IIIb)
- the methyl-substituted alkanol of the formula (IIIb) is presumably formed by reaction of the compound of the formula (II) with .alpha.-methyl-styrene which can be formed in a free-radical reaction from styrene and ethylbenzene according to the following scheme:
- the reaction in step a) takes place under conditions in which the compound of the formula (II) is in the supercritical state.
- the critical temperature Tc is 263 ° C and the critical pressure Pc is 4.2 MPa.
- Supercritical conditions can be adjusted by the skilled person by varying pressure and temperature.
- the temperature required for a sufficient rate of reaction of styrene with a compound of formula (II) is usually at least (T c + 15) ° C, often at least (T c + 65) ° C and especially at least (T c + 85) ° C, where T c is the critical temperature of the compound of formula (II) used.
- T c is the critical temperature of the compound of formula (II) used.
- the temperature in the reaction in step a) does not exceed a value of (T c + 265) ° C, in particular (T c + 165) ° C.
- the reaction in step a) is preferably carried out at elevated pressure, which is generally in the range from 5 to 50 MPa, often in the range from 10 to 30 MPa and in particular in the range from 15 to 25 MPa.
- elevated pressure which is generally in the range from 5 to 50 MPa, often in the range from 10 to 30 MPa and in particular in the range from 15 to 25 MPa.
- the reaction preferably takes place under the autogenous pressure of the reaction mixture prevailing at the desired reaction temperature.
- the reaction time naturally depends on the chosen conditions and the desired conversion and is usually in the range from 30 s to 4 h, in particular in the range from 3 min to 3 h and especially in the range from 5 min to 2.5 h. In one embodiment of the invention, the reaction time is in the range of 0.5 to 4 h, in particular in the range of 1 to 3 h and especially in the range of 1, 5 to 2.5 h. As a rule, the reaction is carried out to the extent that at least 80%, in particular at least 90%, of the reaction residue used in the deficit, which is preferably styrene, has reacted.
- step a) It has proven particularly advantageous to carry out the reaction in step a) at elevated temperatures, ie above (T c + 65) ° C., in particular above (T c + 85) ° C., preferably in the range (T c + 1 15). ° C and (T c + 165) ° C.
- This allows short reaction times, which are usually in the range of 30 s to 30 min, in particular in the range of 3 min to 20 min and especially in the range of 5 min to 15 min. In this way, good selectivities with respect to the target product can be achieved even with high conversion of styrene.
- step a) it has proved to be advantageous to carry out the reaction in step a) in the substantial or complete absence of catalysts, such as free-radical initiators, acids or transition metal compounds.
- catalysts such as free-radical initiators, acids or transition metal compounds.
- Substantial absence means that the concentration of any catalysts is less than 1 g / kg ( ⁇ 1000 ppm), especially less 0.1 g / kg ( ⁇ 100 ppm) based on the total weight of the reaction mixture.
- the reaction of styrene with a compound of the formula (II) in step a) can be carried out in bulk or in a suitable, ie reaction-inert, diluent.
- suitable inert diluents are aprotic organic solvents which have no ethylenically unsaturated double bond, such as aliphatic and alicyclic ethers having preferably 4, 5 or 6 carbon atoms, for example diethyl ether, 1, 2-dimethoxyethane, bis (2-methoxyethyl) ether, 2 Methyltetrahydrofuran and especially tetrahydrofuran; aliphatic and cycloaliphatic saturated hydrocarbons having preferably 5 to 8 carbon atoms, for example pentane, hexane, heptane or octane; Alkyl esters of aliphatic carboxylic acids having preferably 4 to 8 carbon atoms and mixtures of the abovementione
- the reaction in step a) preferably takes place in substance, ie essentially no starting materials other than styrene and the compound of the formula (II), such as, for example, inert solvents, are used for the reaction. Essentially, it means here that styrene and the compound of the formula (II) account for at least 95% by weight, in particular at least 99% by weight, based on the total amount of the components used in step a).
- the reactants used for the reaction ie styrene and the compound of formula (II), production-related small amounts of impurities such as water, ethylbenzene, toluene and the like may contain, the impurities usually less than 5 wt .-%, in particular less account for 1 wt .-%, based on the total amount of the reactants.
- the water content of the reactants used in step a) is not more than 1 wt .-%, based on the total amount of the reactants.
- a compound of the formula (II) is used in large excess, based on styrene, and / or ensures that in the reaction tion zone in which styrene and the compound of formula (II) are brought into contact under reaction conditions, a large excess of the compound of formula (II), based on the styrene present in the reaction zone is present.
- step a) styrene and the compound of the formula (II) are added in a molar ratio of styrene to compound of the formula (II) of at most 1: 5, preferably at most 1:10, in particular at most 1: 30, particularly preferably at most 1:40 and especially at most 1:50 pm.
- styrene and compound of the formula (II) are in a molar ratio in the range from 1: 5 to 1: 200, preferably in the range from 1:10 to 1: 200 , in particular in the range from 1: 30 to 1: 150 or in the range from 1: 30 to 1: 130, more preferably in the range from 1:40 to 1: 100 and especially in the range from 1:50 to 1:90.
- the reaction in step a) can be carried out batchwise (so-called batch mode), i.
- the styrene and the compound of the formula (II) are initially charged in the desired molar ratio in a suitable reactor and brought to the desired reaction conditions and kept under reaction conditions up to the desired conversion.
- the reaction in step a) can also be carried out in the so-called semi-batch mode, i. the main amount, generally at least 80%, in particular at least 90%, of one or both reactants is added to the reactor continuously or in portions over a relatively long period of time, generally at least 50% of the total reaction time.
- At least 80%, especially at least 90%, of the compound of formula (II) used may optionally be introduced together with a portion of the styrene and at least 80%, in particular at least 90%, of the styrene used be fed to the reaction under reaction conditions.
- the reaction in step a) can also be carried out continuously, ie styrene and compound of the formula (II) are fed continuously in the desired molar ratio into a reaction zone and the reaction mixture is withdrawn continuously from the reaction zone.
- the rate at which styrene and compound of the formula (II) are fed to the reaction zone depends on the desired residence time, which in turn depends on the reactor geometry in a known manner and corresponds to the reaction time given above.
- the reaction in step a) can in principle be carried out in all reactors which are suitable for the chosen reaction conditions, preferably in autoclaves which may have devices for mixing the reactants, or in reaction tubes.
- the rate at which styrene is fed in is thereby preferably chosen such that the molar ratio of the unreacted styrene fed into the reaction zone or the reactor to the compound of the formula (II) in the reaction zone is less than 1 during the reaction : 10, in particular not more than 1:40 and especially not more than 1: 50, and for example is in the range from 1:10 to 1: 2000, preferably in the range from 1:40 to 1: 1500 and in particular in the range from 1:50 to 1: 1000.
- the rate at which styrene is fed in is preferably chosen such that the molar ratio of the styrene fed into the reaction zone or reactor to the compound of formula (II) in the reaction zone is in the range of 1 : 10 to 1: 130, in particular in the range from 1:20 to 1: 120, more preferably in the range from 1:40 to 1: 100 and especially in the range from 1:50 to 1:90.
- the reaction mixture obtained in step a) can be worked up in a manner known per se or, if appropriate after removal of the compound of the formula (II), used directly as such in step b) of the process according to the invention.
- the reaction mixture obtained in step a) is worked up by distillation to give the desired compound of formula (IIIa) or the desired composition consisting essentially of the compound of formula (IIIa) and the corresponding compound of the formula (IIIb), as the middle fraction of light and high boilers separated.
- the low-boiling fraction which consists predominantly of compound of the formula (II)
- the compound of the formula (II) is substantially removed before step b), so that the proportion of compound of the formula (II) in the educt used for the hydrogenation in step b) is less than 20% by weight, in particular not more than 10 wt .-%, based on the total amount of starting material in step b).
- the substantially pure compound of the formula (IIIa) is obtained (purity of at least 95% by weight, in particular at least 98% by weight and especially at least 99% by weight or at least 99.5% by weight.
- a catalyst suitable for the nuclear hydrogenation of aromatic substances which is also referred to below simply as a catalyst.
- Suitable catalysts are in principle all catalysts which are known to be suitable for the ring hydrogenation of aromatics, ie catalysts which catalyze the hydrogenation of phenyl groups to cyclohexyl groups.
- These are usually catalysts containing at least one active metal from Group VIIIB of the Periodic Table (CAS version), such as palladium, platinum, cobalt, nickel, rhodium, iridium, ruthenium, in particular ruthenium, rhodium or nickel, or a Mixture of two or more thereof, optionally in combination with one or more other active metals.
- Preferred further active metals are selected from groups IB or VIIB of the periodic table (CAS version). Under the likewise usable metals of subgroups IB and / or VIIB are, for example, copper and / or rhenium.
- the catalysts may be full catalysts or, preferably, support catalysts.
- Suitable support materials are, for example, activated carbon, silicon carbide, silicon dioxide, aluminum oxide, magnesium oxide, titanium dioxide, zirconium oxide, aluminosilicates and mixtures of these support materials.
- the amount of active metal is usually 0.05 to 10 wt .-%, often 0.1 to 7 wt .-% and in particular 0.1 to 5 wt .-%, based on the total weight of the supported catalyst, in particular, if the active metal is a noble metal such as rhodium, ruthenium, platinum, palladium or iridium.
- the amount of active metal can be up to 100% by weight and is usually in the range from 1 to 100% by weight, in particular from 10 to 90% by weight the total weight of the catalyst.
- the supported catalysts can be used in the form of a powder.
- a powder has particle sizes in the range from 1 to 200 ⁇ m, in particular from 1 to 100 ⁇ m.
- Powdered catalysts are particularly suitable when the catalyst is suspended in the reaction mixture to be hydrogenated (suspension mode).
- moldings which are e.g. are obtainable by extrusion, extrusion or tableting and which are e.g. may have the form of spheres, tablets, cylinders, strands, rings or hollow cylinders, stars and the like.
- the dimensions of these moldings usually range from 0.5 mm to 25 mm. Frequently, catalyst strands with strand diameters of 1, 0 to 5 mm and
- Strand lengths of 2 to 25 mm used. With smaller strands generally higher activities can be achieved, but these often do not show sufficient mechanical stability in the hydrogenation process. Therefore, very particularly preferably strands with strand diameters in the range of 1, 5 to 3 mm are used. Also preferred are spherical support materials with ball diameters in the range of 1 to 10 mm, in particular 2 to 6 mm.
- Preferred catalysts are those which comprise at least one active metal selected from ruthenium, rhodium and nickel, optionally in combination with one or more further active metals selected from groups IB, VIIB and VI 11 B of the periodic table (CAS version) ,
- catalysts are ruthenium-containing catalysts. These contain ruthenium as the active metal, optionally in combination with one or more additional active metals. Preferred further active metals are selected from Groups IB, VIIB and VII IB of the Periodic Table (CAS version).
- the catalysts may be full catalysts or, preferably, supported catalysts.
- further active metals from the group VI 11 B are, for example, platinum, rhodium, palladium, iridium, cobalt and nickel, which can also be used as a mixture of two or more thereof.
- the metals of subgroups IB and / or VIIB which can likewise be used, for example copper and / or rhenium are suitable. Ruthenium is preferably used alone as active metal or together with platinum or iridium as active metal; With very particular preference ruthenium is used alone as the active metal.
- ruthenium-containing catalysts in which the ruthenium and the optionally present further active metals are arranged on a support material (ruthenium-containing supported catalysts).
- Suitable support materials for the ruthenium-containing supported catalysts are in principle the abovementioned support materials.
- silicon dioxide-containing carrier materials in particular those which have a silicon dioxide content of at least 90% by weight, based on the total weight of the carrier material.
- alumina-containing carrier materials in particular those which have a content of aluminum oxide (calculated as Al 2 O 3) of at least 90% by weight, based on the total weight of the carrier material.
- the support materials preferably have a BET specific surface area, determined by N 2 adsorption according to DIN 66131, of at least 30 m 2 / g, in particular 50 to 1000 m 2 / g.
- the amount of active metal is usually 0.05 to 10 wt .-%, preferably 0.1 to 3 wt .-% and in particular 0.1 to 1 wt .-%, based on the total weight of the ruthenium-containing supported catalyst.
- Suitable ruthenium-containing catalysts are, for example, those described in US Pat. No. 3,027,398, DE 4407091, EP 258789, EP 813906, EP 1420012, WO 99/32427, WO 00/78704, WO 02/100536, WO 03/103830, WO 2005/61 105, US Pat. WO 2005/61 106, WO 2006/136541 and WO201 1082991 mentioned catalysts. With respect to the catalysts disclosed therein, reference is made to these documents.
- catalysts are rhodium-containing catalysts. These contain rhodium as active metal, optionally in combination with one or more further active metals.
- Preferred further active metals are selected from the groups IB, VIIB or VI 11 B of the periodic table (CAS version).
- the catalysts may be solid catalysts or, preferably, supported catalysts.
- further active metals from the group VI 11 B are, for example, platinum, palladium iridium, cobalt and nickel, which may also be used as a mixture of two or more thereof.
- the metals of subgroups IB and / or VIIB which can likewise be used, for example copper and / or rhenium are suitable.
- rhodium is used alone as the active metal or together with platinum or iridium as the active metal; most preferably, rhodium is used alone as the active metal.
- Suitable rhodium-containing catalysts are known, for example, from the publications mentioned above for ruthenium-containing catalysts, can be prepared by the procedures given there or are commercially available, for example the catalyst Escat 34 from Engelhard.
- the abovementioned support materials can be considered.
- alumina-containing support materials in particular those having a content of alumina (calculated as Al2O3) of at least 90 wt .-%, based on the total weight of the support material.
- the amount of active metal is usually 0.05 to 10 wt .-%, based on the total weight of the rhodium-containing supported catalyst.
- nickel-containing catalysts These contain nickel as the active metal, optionally in combination with one or more further active metals. Preferred further active metals are selected from Groups IB, VIIB or VIIIB of the Periodic Table (CAS version).
- the catalysts may be solid catalysts or, preferably, supported catalysts.
- Examples of further active metals from group VIIIB are, for example, platinum, palladium, iridium and cobalt, which can also be used as a mixture of two or more thereof.
- the metals of subgroups IB and / or VIIB which can likewise be used for example copper and / or rhenium are suitable.
- nickel is preferably used alone as the active metal.
- Suitable nickel-containing catalysts are commercially available, for example the catalyst Ni5249P from BASF SE.
- the abovementioned support materials come into consideration. Preference is given to silica, alumina and magnesium oxide-containing support materials, in particular those which consist of at least 90 wt .-% of such materials.
- the amount of active metal is usually 1 to 90 wt .-%, preferably 10 to 80 wt .-% and in particular 30 to 70 wt .-%, based on the total weight of the nickel-containing supported catalyst. Preference is also given to those nickel-containing catalysts which consist essentially exclusively of active metal, ie whose amount of active metal is more than 90% by weight, for example 90 to 100% by weight.
- a shell catalyst is used, in particular a shell catalyst which comprises ruthenium alone or together with at least one further active metal of subgroups IB, VIIB or VIIIB of the Periodic Table of the Elements in the abovementioned amounts.
- Such shell catalysts are known, in particular, from WO 2006/136541 and in the unpublished EP 09179201.0.
- Such a shell catalyst is a supported catalyst in which the predominant amount of the active metal contained in the catalyst is in the vicinity of the surface of the catalyst.
- the above-mentioned data can be determined by means of SEM (scanning electron microscopy), EPMA
- Preferred coated catalysts have a content of active metal in the range of 0.05 to 1 wt.%, In particular 0.1 to 0.5 wt .-%, particularly preferably 0.25 to 0.35 wt .-%, each based on the Total weight of the catalyst.
- shell catalysts with a support material based on silicon dioxide in general amorphous silicon dioxide, are particularly preferred.
- amorphous is understood in this context that the proportion of crystalline silicon dioxide phases makes up less than 10% by weight of the support material.
- the support materials used for the preparation of the catalysts may have superstructures, which are formed by regular arrangement of pores in the carrier material.
- Suitable support materials are in principle amorphous silicon dioxide types which are at least 90 Wt .-% consist of silicon dioxide, wherein the remaining 10 wt .-%, preferably not more than 5 wt .-%, of the support material may also be another oxidic material, for example MgO, CaO, ⁇ 2, ZrÜ2, Fe2Ü3 and / or alkali metal oxide.
- the support material is halogen-free, in particular chlorine-free, ie the content of halogen in the support material is less than 500 ppm by weight, for example in the range from 0 to 400 ppm by weight.
- a coated catalyst which contains less than 0.05% by weight of halide (determined by ionic chromatography), based on the total weight of the catalyst.
- support materials which have a specific surface area in the range from 30 to 700 m 2 / g, preferably from 30 to 450 m 2 / g (BET surface area to DIN 66131).
- Suitable amorphous support materials based on silicon dioxide are familiar to the person skilled in the art and commercially available (see, for example, OW Flörke, "Silica” in U-IImann's Encyclopedia of Industrial Chemistry, 6th Edition on CD-ROM). They may have been both natural and artificial.
- suitable amorphous support materials based on silica are silica gels,
- the catalysts used silica gels as support materials.
- the support material may have different shapes. If the process according to the invention in which the shell catalysts are used is designed as a suspension process, the support material in the form of a finely divided powder will usually be used to prepare the catalysts used.
- the powder preferably has particle sizes in the range from 1 to 200 ⁇ m, in particular from 1 to 100 ⁇ m.
- the support material of the coated catalyst used which is in particular a support material based on silicon dioxide, a pore volume in the range of 0.6 to
- 1, 0 ml / g preferably in the range of 0.65 to 0.9 ml / g, for example from 0.7 to 0.8 ml / g, determined by Hg porosimetry (DIN 66133), and a BET surface area in the range 280 to 500 m 2 / g, preferably in the range of 280 to 400 m 2 / g, most preferably in the range of 300 to 350 m 2 / g.
- at least 90% of the pores present preferably have a diameter of 6 to 12 nm, preferably 7 to 11 nm, particularly preferably 8 to 10 nm.
- the pore diameter can be determined by methods known to those skilled in the art, for example by Hg porosimetry or N 2 physisorption. In a preferred embodiment, at least 95%, particularly preferably at least 98%, the pores present a pore diameter of 6 to 12 nm, preferably 7 to 1 1 nm, more preferably 8 to 10 nm, on. In a preferred embodiment, there are no pores in these shell catalysts which are smaller than 5 nm. Furthermore, there are preferably no pores in these shell catalysts which are greater than 25 nm, in particular greater than 15 nm. In this context, "no pores" means that no pores with these diameters are found by conventional measuring methods, for example Hg porosimetry or IS physisorption.
- the dispersity of the active metal is preferably from 30 to 60% and more preferably from 30 to 50%.
- Methods for measuring the dispersity of the active metal are known in the art, including, for example, the pulse desorption, in which the determination of the noble metal dispersion (specific metal surface, crystallite size) is carried out with a CO pulse method (DIN 66136 (1 -3)).
- the hydrogenation process according to the invention can be carried out in the liquid phase or in the gas phase.
- the hydrogenation process according to the invention is preferably carried out in the liquid phase.
- the hydrogenation process according to the invention can be carried out both in the presence and in the absence of a solvent or diluent, ie it is not absolutely necessary to carry out the hydrogenation in solution.
- the solvent or diluent used may be any suitable solvent or diluent. Suitable solvents or diluents are in principle those which are able to dissolve the organic compound to be hydrogenated as completely as possible or completely mix with it and which are inert under the hydrogenation conditions, ie are not hydrogenated.
- Suitable solvents are cyclic and acyclic ethers having preferably 4 to 8 carbon atoms, for example tetrahydrofuran, dioxane, methyl tert-butyl ether, dimethoxyethane, dimethoxypropane, dimethyldiethylene glycol, aliphatic alcohols having preferably 1 to 6 carbon atoms, such as methanol , Ethanol, n- or isopropanol, n-, 2-, iso- or tert-butanol, carboxylic esters of aliphatic carboxylic acids having preferably 3 to 8 carbon atoms such as methyl acetate, ethyl acetate, acetic acid propyl ester or butyl acetate, methyl propionate, ethyl propionate, butyl propionate and aliphatic ether alcohols such as methoxypropanol and cycloaliphatic compounds such as cyclohexane,
- step b) according to the invention is carried out in bulk.
- the actual hydrogenation is usually carried out in analogy to the known hydrogenation for the hydrogenation of organic compounds having hydrogenatable groups, preferably for the hydrogenation of a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, as described in the aforementioned prior art.
- the organic compound as a liquid phase or gas phase, preferably as a liquid phase, brought into contact with the catalyst in the presence of hydrogen.
- the liquid phase can be passed over a catalyst fluidized bed (fluid bed mode) or a fixed catalyst bed (fixed bed mode).
- the hydrogenation can be configured both continuously and discontinuously, wherein the continuous process procedure is preferred.
- the process according to the invention is carried out in trickle-bed reactors or in flooded mode according to the fixed-bed procedure, with the implementation in trickle-bed reactors being particularly preferred.
- the compound to be hydrogenated in substance i. largely absence of organic diluents used (solvent content preferably ⁇ 10%).
- the hydrogen can be passed both in cocurrent with the solution of the educt to be hydrogenated and in countercurrent over the catalyst.
- the hydrogenation can also be carried out batchwise by the batch procedure. In this case, the hydrogenation is preferably carried out in an organic solvent or diluent.
- the catalyst is typically used in such an amount in step b) that the concentration of ruthenium in the reaction mixture used for the hydrogenation in the range of 10 to 10,000 ppm, especially in the range of 50 to 5000 ppm, especially in the range of 100 to 1000 ppm.
- the hydrogenation is typically carried out at a hydrogen pressure in the range of 5 to 50 MPa, in particular in the range of 10 to 30 MPa.
- the hydrogen can be fed as such, or diluted with an inert, for example nitrogen or argon in the reactor.
- the hydrogenation in step b) is typically carried out at temperatures above 50 ° C, in particular in the range of 100 to 250 ° C.
- R 1 and R 2 independently of one another are of groups of the formula (C 3-7 -cycloalkyl) x - (C 1-7 -alkyl) y , where either x and y are each 1 or one of the variables x and y 1 and the other is O, are selected and R 1 and R 2 together comprise a total of 4 to 1 1 carbon atoms, 5 to 1 1 carbon atoms, in particular 4 to 8 carbon atoms and preferably 4 or 5 carbon atoms are also provided by the invention. When R 1 and R 2 together comprise a total of 4 carbon atoms, then R 1 and R 2 are preferably each ethyl.
- Compounds of the formula (Ia) according to the invention can therefore be selected, for example, from 1-cyclohexyl-3-methyl-3-heptanol, 1-cyclohexyl-3-methyl-3-octanol, 1 -
- Cyclohexyl-3-methyl-3-nonanol 1-cyclohexyl-3,4-dimethyl-3-octanol, 1-cyclohexyl-3,5-dimethyl-3-octanol, 1-cyclohexyl-3,6-dimethyl-3 octanol, 1-cyclohexyl-3,7-dimethyl-3-octanol, 1-cyclohexyl-3,4,4-trimethyl-3-heptanol, 1-cyclohexyl-3,5,5-trimethyl-3-heptanol, 1 - Cyclohexyl-3,6,6-trimethyl-3-heptanol, 1-cyclohexyl-5-ethyl-3-methyl-3-heptanol, 1-cyclohexyl-3,5-dimethyl-3-heptanol, 2,4-dicyclohexyl 2-methyl-2-butanol, 1-cyclohexyl-4-cyclopenty
- R 1 and R 2 are independently selected from groups of the formula (C 3-7 -cycloalkyl) x - (C 1-7 -alkyl) y , as defined above, and R 1 and R 2 together represent a total of 3 to 1 1 carbon atoms, especially 3 to 8 carbon atoms, preferably 3 to 5 carbon atoms and more preferably 3 carbon atoms.
- compositions typically in the range of 50: 1 to 1000: 1.
- Such compositions may also contain small amounts of a corresponding compound of the formula (IV)
- the proportion by weight of the total amount of the compound of formula (IV) and optionally of the compound of formula (V) is usually not 10 wt .-%, in particular 5 wt .-%, based on the corresponding compound of formula (la) if present, is in the range from 0.01 to 10% by weight, in particular in the range from 0.01 to 5% by weight, based on the corresponding compound of the formula (Ia).
- compositions that are substantially, ie at least 95%, more preferably at least 98% and especially at least 99% or at least 99.5% by weight of a compound of formula (Ia) and small amounts of corresponding compound of formula (Ib), eg compositions wherein the weight ratio of the compound of formula (Ia) to the corresponding compound of formula (Ib) is in the range of 50: 1 to 1000: 1 ,
- compositions in which the weight ratio of the compound of the formula (Ia) to the corresponding compound of the formula (Ib) is outside the ranges mentioned here can be obtained by mixing the compound of the formula (Ia) with the desired amount of compound of the formula (Ib ) getting produced.
- Such compositions are of course also subject of the present invention.
- a compound of formula (Ib) may be prepared from a corresponding compound of formula (IIIb) in analogy to step b), i. by a process comprising a heterogeneous-catalytic hydrogenation of the compound of formula (IIIb).
- the information given above for the hydrogenation in step b) is taken in full reference to the hydrogenation of the compound of formula (IIIb).
- a compound of the formula (IIIb) can be prepared in a targeted manner by reacting ⁇ -methylstyrene with a corresponding compound of the formula (II) under the conditions mentioned above for step a).
- the present invention also relates to the individual enantiomers and enantiomer mixtures, for example a racemate, of the compounds of the formula (Ia) or of the formula (Ib) according to the invention.
- the enantiomers can be separated by well-known methods, for example by crystallization, by chiral column chromatography, or by conversion to diastereomers, which are separated by conventional chromatography and distillation techniques and then converted back to the now enantiomerically pure starting materials.
- the compounds of the formula (Ib) according to the invention may have a different configuration on the chiral carbon atom bearing the cyclohexyl group. Accordingly, the present invention also relates to individual diastereomers and diastereomer mixtures of the compounds of the formula (Ib) according to the invention.
- the diastereomers because of their different physical properties, can be separated by conventional methods, such as chromatography and distillation techniques.
- the invention thus also relates to cosmetic compositions, laundry detergents and hard surface cleaners, comprising:
- compositions comprising a compound of the formula (Ia) and a corresponding compound of the formula (Ib), especially those in which R 1 and R 2 together comprise a total of 3 to 8 carbon atoms and preferably 3 to 5 carbon atoms, more preferably where R is 1 is methyl and R 2 is ethyl.
- R 1 and R 2 together comprise a total of 3 to 8 carbon atoms and preferably 3 to 5 carbon atoms, more preferably where R is 1 is methyl and R 2 is ethyl.
- the compound (s) i. or composition ii. contained as additives ie such cosmetic products, laundry detergents or hard surface cleaning agents contain in addition to i. or ii.
- suitable cosmetic agents are in principle all cosmetic compositions which usually contain fragrances.
- Eaux-de-Parfum, Eaux-de-Toilette, Eaux-de-Cologne, after-shave products such as lotions and creams, pre-shave products, perfumed towelettes, depilatory creams and lotions, tanning creams and lotions, hair care products such as Shampoos, hair conditioners, hair fixatives, hair gels, hair toners, hair waxes, hair sprays, mousses, hair mousses, top fluids, perming agents, hair colorants and bleaching agents or hot oil treatments, and also skin cleansers such as soaps, washing gels, shower gels, body care preparations such as skin creams, oils, lotions, and the like, such as hands, face, or foot care products, sunscreens, deodorants and antiperspirants, skin disinfectants, insect repellents, and decorative cosmetic products.
- the cosmetic compositions can be formulated as aqueous or alcoholic liquid, oil, (aerosol) spray, (aerosol) foam, mousse, gel
- Detergents include agents for cleaning and / or disinfecting surfaces, such as household cleaners, neutral cleaners, toilet cleaners, floor cleaners, carpet cleaners, window cleaners, polishes, furniture care products, liquid and solid dishwashing detergents, liquid and solid machine dishwashing detergents, as well as Cleaning or treatment of textiles such as solid, semi-solid or liquid laundry detergents, laundry aftertreatment agents, softeners, ironing aids, textile removers, fabric preconditioners, laundry soaps, washing tablets and the like.
- agents for cleaning and / or disinfecting surfaces such as household cleaners, neutral cleaners, toilet cleaners, floor cleaners, carpet cleaners, window cleaners, polishes, furniture care products, liquid and solid dishwashing detergents, liquid and solid machine dishwashing detergents, as well as Cleaning or treatment of textiles such as solid, semi-solid or liquid laundry detergents, laundry aftertreatment agents, softeners, ironing aids, textile removers, fabric preconditioners, laundry soaps, washing tablets and the like.
- compositions of the present invention may be used as a perfume ingredient in other perfume-containing products such as air cleaners, lamp oils, candles, room air improvers, WC bricks, and the like.
- the compound of the formula (Ia) in the compositions, cosmetic agents, textile detergents, cleaning compositions and uses according to the invention can be selected, for example, from 1-cyclohexyl-3-methyl-3-pentanol, 1-cyclohexyl-3-methyl-3-hexanol, 1 -Cyclohexyl-3-methyl-3-heptanol, 1-cyclohexyl-3-methyl-3-octanol, 1-cyclohexyl-3-methyl-3-nonanol, 1-cyclohexyl-3,4-dimethyl-3-octanol, 1 -
- the carrier material used was a spherical SiO 2 carrier (type AF125 from BASF SE) with a spherical diameter of 3 to 5 mm and a shaking density of 0.49 kg / l.
- the BET surface area was 337 m 2 / g, the water absorption (WA) at 0.83 ml / g.
- a 14.25 wt .-% solution of ruthenium (III) acetate in acetic acid from Umicore. 200 g of carrier were placed in a round bottom flask. 15 g of the ruthenium acetate
- Solution was diluted to 150 ml with distilled water (90% WA).
- the support material was placed in the distillation flask of a rotary evaporator and the first quarter of the solution was pumped onto the support material at a gentle vacuum at 3 to 6 rpm. After completion of the addition, the support was left in a rotary evaporator at 3 to 6 rpm for a further 10 minutes to homogenize the catalyst. This impregnation homogenization step was repeated three times until all the solution had been applied to the support.
- the thus treated support material was dried in a rotary kiln at 140 ° C, then for 3 h at 200 ° C in a stream of hydrogen (20 l / h H 2 , 10 l / h N 2 ) and passivated at 25 ° C (5% air in N2, 2 h).
- the novel catalyst A obtained in this way contained 0.34% by weight of ruthenium, based on the total weight of the catalyst.
- Step a) - Example 2 Preparation of 3-methyl-1-phenyl-3-pentanol
- the reaction of styrene and 2-butanol was carried out in a continuously operated laboratory plant. This included a 300 ml autoclave operated under pressure control. Thus, the removal amount corresponded at any time of the entry amount.
- the withdrawn reaction mixture was cooled, vented and collected in a discharge vessel.
- the effluent was analyzed by gas chromatography (polydimethylsiloxane DB1, 30 m, internal diameter: 0.25 mm, film thickness: 0.25 ⁇ m, 50 ° C., 5 minutes isothermal, -6 ° C./min, 290 ° C., 219 minutes isothermal) , The conversion was 99.9%, the selectivity at 93%.
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Abstract
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EP13802553.1A EP2925712A1 (fr) | 2012-11-27 | 2013-11-26 | Procédé de production d'alcanols tertiaires cyclohexyl-substitués |
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EP12194445 | 2012-11-27 | ||
PCT/EP2013/074660 WO2014082978A1 (fr) | 2012-11-27 | 2013-11-26 | Procédé de production d'alcanols tertiaires cyclohexyl-substitués |
EP13802553.1A EP2925712A1 (fr) | 2012-11-27 | 2013-11-26 | Procédé de production d'alcanols tertiaires cyclohexyl-substitués |
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Non-Patent Citations (2)
Title |
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I. N. NAZAROV, T. D. NAGIBINA: "The Derivatives of Acetylene. Part 43. Dienic Synthesis on the Basis of Vinylethyinylcarbinols", IZVESTIYA AKADEMII NAUK SSSR, SERIYA KHIMICHESKAYA, 1946, pages 83 - 90, XP008183798 * |
See also references of WO2014082978A1 * |
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