CN1900041A - 通过次氯酸盐使伯醇钌催化氧化成醛的方法 - Google Patents
通过次氯酸盐使伯醇钌催化氧化成醛的方法 Download PDFInfo
- Publication number
- CN1900041A CN1900041A CNA2006101031110A CN200610103111A CN1900041A CN 1900041 A CN1900041 A CN 1900041A CN A2006101031110 A CNA2006101031110 A CN A2006101031110A CN 200610103111 A CN200610103111 A CN 200610103111A CN 1900041 A CN1900041 A CN 1900041A
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- China
- Prior art keywords
- unsubstituted
- group
- iii
- replacement
- alkaline
- Prior art date
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- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title abstract description 18
- 230000003647 oxidation Effects 0.000 title abstract description 17
- 150000001298 alcohols Chemical class 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 37
- -1 alkaline earth metal hypochlorite Chemical class 0.000 claims abstract description 30
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 19
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000002576 ketones Chemical class 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 28
- 239000007787 solid Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000001118 alkylidene group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229940123457 Free radical scavenger Drugs 0.000 description 4
- 229960004217 benzyl alcohol Drugs 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910019093 NaOCl Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000007704 wet chemistry method Methods 0.000 description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 2
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 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 2
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- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
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- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 239000007844 bleaching agent Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical group C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 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
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical class [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([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
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- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- MDTPTXSNPBAUHX-UHFFFAOYSA-M trimethylsulfanium;hydroxide Chemical compound [OH-].C[S+](C)C MDTPTXSNPBAUHX-UHFFFAOYSA-M 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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Abstract
本发明涉及在非均相的无机负载钌催化剂存在下,使用碱金属或碱土金属次氯酸盐水溶液作为氧化剂,使伯醇氧化成醛的方法。
Description
技术领域
本发明涉及在非均相的无机负载钌催化剂存在下,使用次氯酸盐水溶液作为氧化剂,使伯醇氧化成醛的方法。
背景技术
醛是化学工业中重要的有机产品和中间体,例如用于药物和农用化学品的活性成分和用于专用化学品。合成醛的常用方法是氧化相应的伯醇。为此,可使用便宜和易于处理的氧化剂的金属催化的氧化反应在工业中特别重要。与使用化学计量量的金属盐,例如铬(VI)化合物、二氧化锰或高锰酸盐的方法相比,催化方法具有相当的生态学和经济的优点。适合用于催化的醇氧化反应的活性金属是例如钌,它比其它同样适合作为催化剂的金属,例如钯、铂或锇更加便宜和低毒。
Angew.Chem.2002,114,4720-4724(N.Mizuno等)公开了通过分子氧使伯醇氧化成醛的Ru/Al2O3催化剂。RuO2、Ru/C、Ru/CeO2、Ru/水滑石和Ru-羟磷灰石催化剂也可用于此反应。但是,从安全的角度看,分子氧的缺点是能够与其它物质形成可燃或爆炸性混合物。
R.A.Sheldon等,Org.Lett.2002,4,1659和Adv.Synth.Catal.2003,345,1321,以及G.Balavoine等,J.Mol.Catal.1985,30,125公开了优选均相的催化剂体系,其中Ru化合物如过钌酸四正丙基铵(n-Pr4NRuO4)或RuCl2(配体)2等,与次氯酸钠一起用作氧化剂。但是,这些工艺的缺点是用次氯酸钠作为氧化剂,伯醇以仅仅非常低的选择性转化成各自的醛。而且,均相催化剂体系与非均相催化剂体系相比的缺点是,从产物的分离和再循环更加困难(参见Tetrahedron Letters 2000,41,3971-3974)。
Tetrahedron Letters 2000,41,3971~3974描述了使用聚(4-乙烯基吡啶)负载的钌催化剂,使醇氧化成醛或酮。但是,它没有表明,便宜和易于处理的氧化剂如NaOCl适合于此方法。此外,这种聚合物负载的催化剂的缺点是,负载聚合物自身必须在制备催化剂之前已经制备,或者如果它们是可商业购得的,它们比常规无机载体材料更加昂贵。而且,这种有机聚合物载体材料可能缺乏对氧化剂的抗性。
发明内容
因此,持续需要以高选择性使醇氧化成醛的催化方法,该方法没有上述缺点。
因此,本发明的目的是提供使伯醇催化氧化成醛的简单方法,其中使用便宜、容易处理的氧化剂,以高选择性获得目标产物。本发明的另一目的是提供用于这种方法的合适催化剂。
在本发明中,现在已经发现,可在非均相的无机负载钌催化剂存在下,并在碱金属次氯酸盐或碱土金属次氯酸盐作为氧化剂存在下,有效地将伯醇选择性氧化成醛。这是令人惊奇的,因为在使用次氯酸盐作为氧化剂的伯醇的催化氧化反应中,选择性形成醛是不能预期达到的。而且,不能预期获得高效率,因为例如从Angew.Chem.2002,114,4720-4724已知,非均相Ru-催化的氧化反应经常以低转换数(TONs)进行,并对底物(substrate)的选择有限制。
因此本发明提供制备通式(I)的醛和酮的方法,
其中
R为氢原子
或取代或未取代的烃基团,其可为烷基基团、环烷基基团、链烯基基团、芳基基团、芳烷基基团或芳烯基基团,它们在各自的情况下具有1~20个碳原子,可优选被至少一个取代基取代,该取代基选自卤素原子、硝基、烷氧基、芳氧基、尤其是苯氧基、芳基、烷基和酰氧基,
或取代或未取代的杂环基团,其优选具有至少一个选自氧、氮和硫的杂原子。
该方法的特征在于使通式(II)的化合物,
其中R为如上所定义的。
与碱金属次氯酸盐或碱土金属次氯酸盐反应。作为底物的醇可为一元醇或多元醇,并且可使用两种或多种这些醇的混合物。如果醇或一种醇为多元醇,其中存在的羟基基团可被部分或完全氧化成对应的醛基团,所得的产物可为对应的多羰基化合物或仍包含羟基基团的单羰基或多羰基化合物。如果醇或醇的一种为多元醇,它们具有通式(II-a),
其中R’具有对R给出的含义,条件是存在于R’中的任何羟基取代基被全部或部分氧化成通式(I)的目标化合物中的羰基取代基。尤其优选的多元醇是二元醇,如取代或未取代的乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇或1,10-癸二醇。
下文中,除非另外说明,将基团R’归入R下。
在非均相的无机负载钌催化剂存在下进行反应,该催化剂可另外掺杂另一过渡金属TM。这种非均相的无机负载钌催化剂优选由通式(IIIa)或(IIIb)表示:
Ru/载体(IIIa) Ru/TM/载体(IIIb)
本发明的范围包括以上给出的所有一般的或优选的基团定义、参数和说明,或在下文中彼此的任何组合,即各自的范围和优选范围之间的组合。
出于本发明的目的,除非另外说明,术语芳基优选是指具有6~24个骨架碳原子的碳环芳香基团,或具有5~24个骨架碳原子的杂芳香基团,其中每个环没有骨架碳原子,或有一个、两个或三个骨架碳原子,但是整个分子中至少有一个骨架碳原子,可被选自氮、硫和氧的杂原子取代。而且,碳环芳香基团或杂芳香基团的每个环可被至多5个相同或不同的取代基取代,该取代基选自羟基、卤素、硝基、氰基、自由或被保护的甲酰基、C1-C12-烷基、C1-C12-卤烷基、C5-C14-芳基、C6-C15-芳烷基、C1-C12-烷氧基、C1-C12-烷氧基羰基、取代或未取代的C1-C12-烷基氨基或C1-C12-烷氧基羰基氨基,例如叔丁氧基羰基氨基(BOC-氨基)、羧基、羰基、C1-C12-烷基羧基、巯基、C1-C12-酰基、取代或未取代的C1-C12-氨基羰基、C1-C12-酰氧基羰基和C1-C12-烷基硫基。
同样的适用于芳烷基基团的芳基部分。
例如,芳基尤其优选为苯基、萘基或蒽基,其可被独立地选自C1-C6-烷基、C1-C6-卤代烷基、C5-C14-芳基、C1-C6-烷氧基、C1-C6-烷氧基羰基、卤素、羟基、硝基和氰基的基团单取代、双取代或三取代。
出于本发明的目的,除非另外说明,术语烷基或亚烷基或烷氧基优选在各自的情况下独立地是指取代或未取代的直链、环、支链或非支链的烷基或亚烷基或烷氧基基团。同样的适用于芳烷基基团的亚烷基部分。烷基或亚烷基或烷氧基基团的可能取代基是例如C1-C6-烷基、C1-C6-卤代烷基、C5-C14-芳基、C6-C15-芳烷基、C1-C6-烷氧基、C5-C14-芳氧基、C1-C6-烷氧基羰基、C1-C6-酰氧基、取代或未取代的C1-C12-烷基氨基或C1-C12-烷氧基羰基氨基,例如叔丁氧基羰基氨基(BOC-氨基)、羧基、羰基、C1-C12-烷基羧基、C1-C12-酰基、取代或未取代的C1-C12-氨基羰基、C1-C12-酰氧基羰基或C1-C12-烷基硫基、卤素、羟基、硝基或氰基。
例如,烷基尤其优选为取代或未取代的甲基、乙基、正丙基、异丙基、正丁基、叔丁基、正戊基、环己基和正己基、正庚基、正辛基、异辛基、正癸基和正十二基。
例如,亚烷基优选为取代或未取代的亚甲基、1,1-亚乙基、1,2-亚乙基、1,1-亚丙基、1,2-亚丙基、1,3-亚丙基、1,1-亚丁基、1,2-亚丁基、2,3-亚丁基和1,4-亚丁基、1,5-亚戊基、1,6-亚己基、1,1-环亚己基、1,4-环亚己基、1,2-环亚己基和1,8-亚辛基。
例如,烷氧基优选为甲氧基、乙氧基、异丙氧基、正丙氧基、正丁氧基、叔丁氧基和环己氧基。
环烷基基团可为具有总共3~20个碳原子的3-至7-元同素环或杂环,后者优选具有1、2或3个杂原子。同素环烷基基团例如为取代或未取代的环戊基或环己基;杂环烷基基团的例子为二氧戊环或邻苯二甲酰亚胺基团。
出于本发明的目的,除非另外说明,术语芳烷基优选在各自的情况下独立地是指直链、环、支链或非支链的烷基基团,其被如上所定义的芳基基团单取代或多取代,尤其优选单取代。芳烷基基团的例子是苄基。
出于本发明的目的,除非另外说明,术语卤代烷基或卤代亚烷基优选在各自的情况下独立地是指直链、环、支链或非支链的烷基基团,其可被独立地选自氟、氯、溴和碘的卤素原子单取代、多取代或完全取代。
例如,C1-C8-卤代烷基尤其优选为三氟甲基、三氯甲基、2,2,2-三氟乙基、五氟乙基和九氟丁基。
卤素可为氟、氯、溴或碘,优选氟或氯。
优选的通式(I)、(II)和(III)的化合物定义如下。
在通式(I)和(II)中,R1和R2各自彼此独立地优选为氢、取代或未取代的C1-C20-烷基、取代或未取代的C1-C20-链烯基、取代或未取代的C5-C14-芳基、取代或未取代的C6-C15-芳烷基、取代或未取代的C1-C20-卤代烷基、取代或未取代的C3-C20-环烷基、或取代或未取代的C3-C20-环烯基。
此处尤其优选通式(I)和(II)的化合物,其中R为氢、取代或未取代的C5-C14-芳基、取代或未取代的C1-C20-烷基、或取代或未取代的C1-C20-链烯基。在本发明的优选实施方案中,基团R为取代或未取代的C5-C14-芳基。
基团R的尤其优选的取代基是甲基、乙基、甲氧基、乙氧基、氟、氯、三氟甲基、硝基、苯基、苯氧基和叔丁氧基羰基氨基(BOC-氨基)。如果通式(II)的醇为通式(II-a)的多元醇,基团R’的另一优选取代基为羟基,基团R的另一优选取代基为羰基。
在通式(IIIa)和(IIIb)中,“载体”优选为多孔无机固体。载体尤其优选为选自活性炭、氧化铝、硅酸铝、二氧化硅、硫酸钡、碳酸钙、二氧化铈、二氧化钛和二氧化锆的多孔无机固体。载体尤其优选为活性炭、二氧化钛和二氧化锆。
在通式(IIIb)中,TM优选为过渡金属,尤其优选为选自Cu、Mo、Mn、Fe、Co的过渡金属。
在优选实施方案中,本发明的方法在水和/或一种或多种有机溶剂的存在下进行,该有机溶剂尤其是,例如叔醇、质子惰性的极性溶剂、酮、氯化烃和芳香烃。出于本发明的目的,质子惰性的极性溶剂是在25℃下介电常数为5或以上,并在25℃下以水的参考标度为基准的pKa为20或以上的溶剂。在本发明的方法中,尤其优选水、叔醇,尤其是例如叔戊醇和叔丁醇,以及氯化烃如1,2-二氯乙烷、二氯甲烷、氯仿、氯苯和二氯苯,例如1,2-、1,3-或1,4-二氯苯。在非常尤其优选的实施方案中,该方法在两相混合物中进行,尤其优选在水和1,2-二氯乙烷的存在下进行。
例如,通过最初将通式(I)的化合物和钌催化剂装入溶剂中,使它们与可溶于水的碱金属次氯酸盐或碱土金属次氯酸盐混合,并搅拌混合物至多(upto)24小时的时间,优选至多5小时,尤其优选1小时而进行反应。在优选实施方案中,在5分钟~24小时,优选5小时,尤其优选1小时的时间内,将氧化剂的溶液计量加入到反应混合物中。任何额外的搅拌时间可为例如至多24小时,优选至多5小时,尤其优选至多1小时。
反应可在-20℃~150℃的温度下进行,优选0~80℃,尤其优选0℃~40℃,非常尤其优选15℃~30℃。
反应过程中的压力并不重要,压力可为例如0.5~100bar,尤其是0.8~10bar。尤其优选环境压力。
当碱金属次氯酸盐或碱土金属次氯酸盐用作氧化剂时,优选使用次氯酸钠或次氯酸钾或次氯酸钙氯化物(calcium bypochlorite chloride),例如后者为纯的形式或工业级氯化石灰的形式。尤其优选使用次氯酸钠。氧化剂的用量优选为0.5~10摩尔当量,以通式(II)的化合物为基准,尤其优选1~5摩尔当量,非常尤其优选1~3摩尔当量。如果合适的话,氧化剂优选以溶液和/或溶剂中的悬浮液使用,尤其优选以溶液和/或水以及如果合适的话,额外至少一种上述有机溶剂中的悬浮液使用。
反应可在中性pH下或在酸性或碱性条件下进行;添加酸或碱也是有利的。反应优选在碱性条件下进行,尤其优选在20℃下测量的10~13的pH值下进行。
可选择尤其是通式(IIIa)或(IIIb)的无机负载的钌化合物的用量,使得以通式(II)的醇为基准的钌的量为0.0001~100摩尔%,优选0.01~10摩尔%,尤其优选0.5~1摩尔%。
无机负载的钌催化剂例如可以简单方式通过过滤或离心分离从反应混合物中分离出。如果合适的话,在它可重复使用于反应中之前,可用水和/或有机溶剂洗涤。
可优选向反应中添加少量合适的自由基清除剂。这种合适的自由基清除剂对本领域技术人员是已知的;可提及的例子为氢醌。优选自由基清除剂的用量为至多1当量,以催化剂的金属含量为基准。通过添加这种自由基清除剂,可避免可能的羧酸过氧化,但是这种添加不是绝对必需的。
在根据本发明的温和条件下,可以非常高的选择性获得通式(I)的化合物。后处理(work-up)可以本身已知的方式进行,例如通过用合适的有机溶剂萃取和醛的蒸馏或重结晶。未反应的原料可被循环至方法中。
出于本发明的目的,使用非均相的无机负载钌催化剂,其可另外被一种或多种过渡金属掺杂。
钌的含量可为0.01~20重量%,优选0.05~5重量%。任何另外的过渡金属或存在的金属的含量可为0.01~20重量%,优选0.1~5重量%。钌的含量和过渡金属的含量以催化剂的总质量为基准。各个金属的含量可通过例如ICP-OES(电感耦合等离子体-光发射光谱法)来确定。测定可在例如来自Perkin Elmer的Optima 3000 XL仪器和来自CE Instruments的EA 1110仪器上进行。
在催化剂中,尤其是通式(IIIa)和(IIIb)的催化剂中,钌可以0~+VII的正式氧化态存在,优选0和+III的氧化态,尤其优选+III的氧化态。钌的氧化态例如可通过XPS([Ru3d5/2能级]的结合能)确定。XPS测定例如可在VGESCALAB 220 i XL上进行,使用AlKα辐射(1486.8eV)。这种仪器对本领域技术人员是公知的。为了确定电子结合能,选择284.4eV下的C1s作为参考点。
在本发明方法的优选实施方案中,在通式(IIIa)和(IIIb)的催化剂中,载体上钌颗粒的直径为20nm或以下,其可用透射电子显微镜(TEM)确定。在本发明方法的尤其优选的实施方案中,载体上钌颗粒的直径为2nm或以下。TEM测定例如可使用Phillips CM-20仪器在200kW的加速功率下进行。
用作无机载体的材料的性质如BET表面积不受任何限制。对于二氧化钛,可使用例如来自Degussa的P25(BET表面积:50m2/g±15m2/g)或来自Kronos的TiO2(BET表面积:307m2/g)。对于二氧化锆,可使用例如来自MEL Chemicals的Zr(OH)4MELCAT XZ0631/01(BET表面积:459m2/g)。BET表面积的测定可例如通过ASAP 2000-Mg作为吸附体系在77℃下进行。这种仪器对本领域技术人员是公知的。
可通过例如湿式化学浸渍,使用基于Mizuno等,Angew.Chem.2002,114,4720的方法,将特定量的钌(III)前体例如氯化钌(III),如果合适的话,以及特定量的一种或多种过渡金属化合物,例如硫酸亚铁(II)或氯化钴(II),与合适的溶剂例如水一起放在反应容器中,搅拌的同时添加载体,从而制备通式(IIIa)或(IIIb)的无机负载的钌催化剂,其可被一种或多种过渡金属掺杂。然后从液相中分离出固体,例如通过过滤或离心分离。如果合适的话,用水洗涤固体并干燥。然后将固体悬浮在水中,使所得的混合物变为碱性,例如通过稀释的氢氧化钠溶液。在搅拌多个小时之后,从液相中分离出固体,例如通过过滤或离心分离。如果合适的话,用水洗涤固体并干燥。
在改进的湿式化学制备方法中,也可通过将过渡金属化合物与水一起放在反应容器中,搅拌的同时添加无机负载的钌催化剂,来制备用一种或多种过渡金属掺杂的通式(IIIb)的无机负载的钌催化剂。包括分离固体、洗涤、干燥、悬浮在水中、设为碱性pH、固体分离、洗涤和干燥的进一步步骤,如前面部分中所述的进行。
也可通过MPECVD(微波等离子体增强的化学气相沉积)方法,例如在Ilmplac1200微波等离子体仪器中,进行通式(IIIa)或(IIIb)的无机负载的钌催化剂的制备,其可被一种或多种过渡金属掺杂。例如可通过将特定量的钌(III)前体例如乙酰丙酮钌(III),如果合适的话,以及特定量的一种或多种过渡金属化合物,例如乙酰丙酮钴(II),与特定量的载体一起放在MPECVD仪器中,来进行这种变体方法。例如可在低压氧等离子体中使钌物类,如果合适的话,以及另外的过渡金属物类沉积在载体上,如果合适的话随后可用氢等离子体处理。
通式(IIIa)和(IIIb)的催化剂的例子是式(III-1)~(III-12)的化合物。在被负载的催化剂的缩写中,W代表湿式化学制备方法,P代表等离子体化学制备方法,应用于载体上的各个金属后面的数字表示该金属负载的重量百分比,以催化剂的总质量为基准。括号中的名称/数字是载体材料的商品名。
编号 | 催化剂 |
III-1 | W-Ru 0.83/TiO2(Kronos) |
III-2 | W-Ru 0.50/TiO2(P25) |
III-3 | W-Ru 1.36/TiO2(P25) |
III-4 | W-Ru 1.57/TiO2(P25) |
III-5 | W-Ru 1.9/TiO2(P25) |
III-6 | W-Ru 2.13/ZrO2 |
III-7 | W-Ru 1.85/Cu 0.18/TiO2(P25) |
III-8 | W-Ru 1.1/Fe 0.30/TiO2(P25) |
III-9 | W-Ru 0.45/Co 0.36/TiO2(P25) |
III-10 | W-Ru 0.44/Mn 0.35/TiO2(P25) |
III-11 | P-Ru 0.2/TiO2(P25) |
III-12 | P-Ru 0.34/TiO2(P25) |
III-13 | P-Ru 1.57/TiO2(P25) |
III-14 | P-Ru 0.32/Co 0.51/TiO2(P25) |
而且,使用可商业购得的负载钌/活性炭催化剂:
III-15:H 101 R/W(5% Ru/C;Degussa)
III-16:Escat 440(5% Ru/C;Engelhard)
III-17:K-0402(5% Ru/C;Heraeus)
而且,使用可商业购得的负载钌/Al2O3催化剂:
III-18:K-0453(5% Ru/Al2O3;Heraeus)
可根据本发明制备的通式(I)的化合物对于制备药物或农业化学活性成分、聚合物、专用化学品或其中间体特别有用。
在本发明的方法中,伯醇的氧化在非常温和的条件下进行,使用便宜的碱金属次氯酸盐或碱土金属次氯酸盐,尤其是次氯酸钠(漂白剂),作为具有高化学选择性的氧化剂,并且以非常高的选择性得到相应的醛。尤其要指出的是,需要非常少量的无机负载的钌催化剂,其可以简单的方式从反应混合物中分离出来,并重新用于反应。同时,能够使用便宜的碱金属次氯酸盐或碱土金属次氯酸盐,尤其是次氯酸钠(氯漂白剂),作为氧化剂是非常有利的。
具体实施方式
以下实施例说明本发明,并且不被认为是限制。
实施例
通过XPS测定,在VG ESCALAB 220 i XL上使用AlKα辐射(1486.6eV),来测定[Ru3d5/2能级]的结合能。选择284.4eV下的C1s信号作为测定的参考点。
通过TEM测定,使用Philips CM-20仪器在200kW的加速功率下,测定钌颗粒的直径。
通过ICP-OES,在来自Perkin Elmer的Optima 3000XL仪器或来自CEInstruments的EA 1110仪器上,测定各个金属(金属负载)的含量。
通过ASAP 2000-Mg作为吸附体系在77℃下进行BET表面积的测定。
实施例1:制备催化剂III-1~III-8的一般方法。
将RuCl3或RuCl3·xH2O,如果合适的话,与过渡金属化合物一起溶于特定量的水中,搅拌的同时添加载体。搅拌悬浮液15分钟,然后在7000rpm下离心分离。将上层清液滗析出,用水洗涤残余的固体,再次离心分离。再重复这一洗涤步骤两次,从而获得无色的洗涤液。在室温和减压下干燥固体24~48小时,然后在研钵中磨碎。然后将固体悬浮于90~180ml的水中,使用氢氧化钠水溶液(1mol)使混合物的pH值为13.2。搅拌24小时之后,离心分离该混合物,用水洗涤残余的固体3次。在室温下干燥固体24小时,然后在50℃和减压下干燥4小时。
催化剂III-1:103mg的RuCl3;2g的TiO2(Kronos);60ml的水;产量1.87g。
催化剂III-2:152mg的RuCl3·xH2O;10g的TiO2(P25);180ml的水;产量8.12g。
催化剂III-3:304mg的RuCl3·xH2O;10g的TiO2(P25);180ml的水;产量7.99g。
催化剂III-4:516mg的RuCl3;10g的TiO2(P25);180ml的水;产量8.20g。
催化剂III-5:516mg的RuCl3;10g的TiO2(P25);300ml的水;产量7.33g。
催化剂III-6:310mg的RuCl3;6g的ZrO2;180ml的水;产量4.87g。
催化剂III-7:103mg的RuCl3;10mg的CuCl;2g的TiO2(P25);60ml的水;产量1.85g。
催化剂III-8:103mg的RuCl3;32mg的FeSO4·7H2O;2g的TiO2(P25);60ml的水;产量1.49g。
表1:催化剂III-1~III-8的特性
编号 | 金属负载[重量%] | Ru颗粒的直径[nm] | BET表面积[m2/g] | 结合能[eV] |
III-1 | Ru 0.83 | ≤1 | 253.8 | [Ru3d5/2]282.5 |
III-2 | Ru 0.50 | ≤2 | 55.4 | [Ru3d5/2]282.1 |
III-3 | Ru 1.36 | n.d. | 53.6 | n.d. |
III-4 | Ru 1.57 | 1~5 | 57.9 | [Ru3d5/2]282.1 |
III-5 | Ru 1.90 | ≤1~2 | 62.8 | [Ru3d5/2]281.5 |
III-6 | Ru 2.13 | ≤2 | 433.5 | [Ru3d5/2]281.8 |
III-7 | Ru 1.85;Cu 0.18 | n.d. | 57.2 | [Ru3d5/2]281.8[Cu2p3/2]929.7 |
III-8 | Ru 1.1;Fe 0.30 | n.d. | 55.0 | n.d. |
n.d.=未测定
测定的结合能在氧化态+III钌的特性范围内。
实施例2:催化剂III-9和III-10的制备。
将特定量的钴化合物或锰化合物溶于水中,搅拌的同时添加4g催化剂III-2[W-Ru 0.50/TiO2(P25)]。搅拌悬浮液24小时,然后在7000rpm下离心分离。将上层液体滗析出,用水洗涤残余的固体,再次离心分离。再重复这一洗涤步骤两次。在室温和减压下干燥固体25小时,然后在研钵中磨碎。然后将固体悬浮于90ml的水中,使用氢氧化钠水溶液(1M)使混合物的pH值为13.2。搅拌24小时之后,离心分离该混合物,用水洗涤残余的固体3次。在室温下和减压下干燥固体24小时。
催化剂III-9:292mg的Co(OAc)2·4H2O;产量3.47g。
催化剂III-10:288mg的Mn(OAc)2·4H2O;产量3.34g。
表2:催化剂III-9和III-10的特性
编号 | 金属负载[重量%] | Ru颗粒的直径[nm] | BET表面积[m2/g] | 结合能[eV] |
III-9 | Ru 0.45;Co 0.36 | ≤2 | 52.9 | [Ru3d5/2]282.1[Co2d3/2]780.5 |
III-10 | Ru 0.44;Mn 0.35 | ≤2 | 58.5 | [Ru3d5/2]282.2[Mn2p3/2]640.9 |
n.d.=未测定
测定的结合能在氧化态+III钌的特性范围内。
实施例3:催化剂III-11~III-14的等离子体化学制备。
将特定量的乙酰丙酮钌(III),在催化剂III-14的情况下,以及特定量的乙酰丙酮钴(II),与3g二氧化钛(P25)一起放在MPECVD仪器(Ilmplac 1200微波等离子体仪器)中。随后设定10Pa的真空。在300cm3/min的氧气流和300W的微波功率下点燃等离子体。另外用氢等离子体处理催化剂III-13。
催化剂III-11:84mg的乙酰丙酮钌(III)
催化剂III-12:167mg的乙酰丙酮钌(III)
催化剂III-13:240mg的乙酰丙酮钌(III)
催化剂III-14:120mg的乙酰丙酮钌(III);77mg的乙酰丙酮钴(II)
表3:催化剂III-11~III-14的特性
编号 | 金属负载[重量%] | Ru颗粒的直径[nm] | BET表面积[m2/g] | 结合能[eV] |
III-11 | Ru 0.2 | ≤5 | 60.2 | [Ru3d5/2]280.6 |
III-12 | Ru 0.34 | 1~10 | 59.4 | [Ru3d5/2]280.3 |
III-13 | Ru 1.57 | 1.5~10 | 58.7 | [Ru3d5/2]280.7 |
III-14 | Ru 0.32;Co 0.51 | 1~10 | 59.6 | [Ru3d5/2]282.3[Co2d3/2]780.5 |
n.d.=未测定
对催化剂III-11、III-12和III-13测定的结合能稍高于氧化态0的钌的特性范围,由此可推断,催化剂III-11、III-12和III-13中的大部分钌以金属钌形式存在。对催化剂III-14测定的结合能由于存在促进剂金属Co而增加,从而将这种增加考虑在内,该值同样表明氧化态0的钌,即大部分钌以金属钌存在。
实施例4:使用次氯酸钠将伯醇氧化成醛的一般性实验描述。
将1mmol的各种醇与7ml的各种溶剂一起置于反应烧瓶中,搅拌的同时添加催化剂。使用次氯酸钠水溶液(来自Sigma-Aldrich,10~13%的活性氯)作为氧化剂,通过注射泵将其在60分钟的时间内计量加入到反应混合物中。再搅拌混合物一定时间。随后通过用1,2-二氯乙烷三次萃取分离出有机组分。用气相色谱法分析合并的有机相。在装有HP5柱和质量选择探测器(HP 5971 A)的Hewlett Packard HP 5890仪器上进行气相色谱法。二乙二醇二正丁醚用作内标物。为了检测形成的任何羧酸,在测定之前向分析样品中加入氢氧化三甲基锍。
根据一般的实验描述(实施例4)进行下表中列出的所有的实验。
表4:使用各种催化剂、溶剂和NaOCl的量氧化苄醇
催化剂 | Ru[mmol] | 溶剂 | NaOCl[mmol] | 转化率[%] | 醛的选择性[%] | 苯甲酸的选择性[%] |
III-5 | 0.01 | 3.5ml的水/3.5ml的t-BuOH | 1.1 | 44 | >99 | 0 |
III-5 | 0.01 | 3.5ml的水/3.5ml的t-BuOH | 1.1 | 66 | >99 | 0 |
III-5 | 0.01 | 7ml的t-BuOH | 1.1 | 42 | 90 | 9 |
III-5 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.1 | 83 | >99 | 0 |
III-5 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.1a | 76 | 96 | 3 |
III-5 | 0.005 | 3.5ml的水/3.5ml的DCE | 1.1a | 77 | >99 | 0 |
III-1 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.1 | 74 | 98 | 1 |
III-6 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.1 | 77 | 98 | 1 |
III-12 | 0.005 | 3.5ml的水/3.5ml的DCE | 1.1 | 47 | 50 | 49 |
III-7 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.1 | 75 | 97 | 3 |
III-8 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.1 | 72 | 97 | 3 |
III-9 | 0.005 | 3.5ml的水/3.5ml的DCE | 1.1 | 38 | 50 | 50 |
III-10 | 0.005 | 3.5ml的水/3.5ml的DCE | 1.1 | 85 | 87 | 13 |
III-5 | 0.01 | 3.5ml的水/3.5 | 1.3 | 85 | 95 | 5 |
ml的DCE | ||||||
III-5 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.5 | 100 | 86 | 14 |
III-5 | 0.01 | 3.5ml的水/3.5ml的DCE | 2 | 100 | 74 | 26 |
III-1 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.5 | 80 | 97 | 2 |
III-6 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.5 | 90 | 98 | 2 |
III-7 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.5 | 97 | 94 | 6 |
III-15 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.1 | 55 | 99 | 1 |
III-16 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.1 | 57 | 96 | 3 |
III-17 | 0.01 | 3.5ml的水/3.5ml的DCE | 1.1 | 66 | 99 | 1 |
III-18 | 0.005 | 7ml的t-BuOH | 1.1 | 19 | 99 | 0 |
反应条件:1mmol的苄醇,室温,进一步的搅拌时间:10min;
a进一步的搅拌时间:130min,DCE=1,2-二氯乙烷。
表5:在各种pH值下氧化苄醇
催化剂 | Ru[mmol] | 溶剂 | pH | 转化率[%] | 醛的选择性[%] | 苯甲酸的选择性[%] |
III-5 | 0.01 | 3.5ml的缓冲剂/3.5ml的DCE | 9 | 65 | 95 | 6 |
III-5 | 0.01 | 3.5ml的缓冲剂/3.5ml的DCE | 10 | 65 | 96 | 5 |
III-5 | 0.01 | 3.5ml的缓冲剂/3.5ml的DCE | 11 | 73 | 95 | 5 |
III-5 | 0.01 | 3.5ml的缓冲剂/3.5ml的DCE | 12 | 67 | 96 | 4 |
III-5 | 0.01 | 3.5ml的缓冲剂/3.5ml的DCE | 13 | 64 | 95 | 6 |
反应条件:0.005mmol的Ru,1mmol的苄醇,室温,进一步的搅拌时间:10min;DCE=1,2-二氯乙烷。
表6:使用催化剂III-5[W-Ru 1.9/TiO2(P25)]氧化各种醇
反应条件:0.005mmol的催化剂III-5,1mmol的醇,3.5ml的水/3.5ml的1,2-二氯乙烷,室温,进一步的搅拌时间:10min。
Claims (8)
1、制备通式(I)的醛的方法,
其中
R为氢原子或
取代或未取代的烃基团,其可为烷基基团、环烷基基团、链烯基基团、芳基基团、芳烷基基团或芳烯基基团,它们在各自的情况下具有1~20个碳原子,或
取代或未取代的杂环基团,其优选具有至少一个选自氧、氮和硫的杂原子,或
其中使一种或多种通式(II)的化合物,
其中R为如上所定义的,
与碱金属次氯酸盐或碱土金属次氯酸盐在非均相的无机负载钌催化剂存在下反应,该催化剂可另外掺杂另一过渡金属。
2、根据权利要求1的方法,其中使用的非均相的无机负载钌催化剂是通式(IIIa)或(IIIb)的催化剂
Ru/载体(IIIa) Ru/TM/载体(IIIb),
其中
TM为过渡金属,并且
载体为无机载体材料。
3、根据权利要求1的方法,其中选自活性炭、氧化铝、硅酸铝、二氧化硅、硫酸钡、碳酸钙、二氧化铈、二氧化钛和二氧化锆的多孔无机固体用作载体。
4、根据权利要求1的方法,其中R优选为氢、取代或未取代的C1-C20-烷基、取代或未取代的C1-C20-链烯基、取代或未取代的C5-C14-芳基、取代或未取代的C6-C15-芳烷基、取代或未取代的C1-C20-卤代烷基、取代或未取代的C3-C20-环烷基、或取代或未取代的C3-C20-环烯基。
5、根据权利要求1的方法,其中基团R为取代或未取代的C5-C14-芳基。
6、根据权利要求1的方法,其中反应在水和/或一种或多种有机溶剂的存在下进行,该有机溶剂尤其是,例如叔醇、质子惰性的极性溶剂、酮、氯化烃和芳香烃。
7、根据权利要求1的方法,其中使用次氯酸钠或次氯酸钾或次氯酸钙氯化物作为碱金属次氯酸盐或碱土金属次氯酸盐。
8、根据权利要求1的方法,其中所述碱金属次氯酸盐或碱土金属次氯酸盐的用量为0.5~10摩尔当量,以通式(II)的化合物的摩尔量为基准。
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