CN1642892A - 将醇转化为羰基化合物的方法 - Google Patents
将醇转化为羰基化合物的方法 Download PDFInfo
- Publication number
- CN1642892A CN1642892A CNA038073803A CN03807380A CN1642892A CN 1642892 A CN1642892 A CN 1642892A CN A038073803 A CNA038073803 A CN A038073803A CN 03807380 A CN03807380 A CN 03807380A CN 1642892 A CN1642892 A CN 1642892A
- Authority
- CN
- China
- Prior art keywords
- cucl
- phenanthrolene
- alkali
- mantoquita
- pyridyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000001728 carbonyl compounds Chemical class 0.000 title claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 title abstract 3
- -1 copper complex salt Chemical class 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 27
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 150000004699 copper complex Chemical class 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- ANJHKVLUGKEZJB-UHFFFAOYSA-N 2,4-ditert-butyl-6-(3,5-ditert-butyl-2-hydroxyphenyl)sulfanylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(SC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O ANJHKVLUGKEZJB-UHFFFAOYSA-N 0.000 claims description 2
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 claims description 2
- KNVZVRWMLMPTTJ-UHFFFAOYSA-N 2-(3-carboxy-2-pyridinyl)-3-pyridinecarboxylic acid Chemical compound OC(=O)C1=CC=CN=C1C1=NC=CC=C1C(O)=O KNVZVRWMLMPTTJ-UHFFFAOYSA-N 0.000 claims description 2
- XPQIPUZPSLAZDV-UHFFFAOYSA-N 2-pyridylethylamine Chemical compound NCCC1=CC=CC=N1 XPQIPUZPSLAZDV-UHFFFAOYSA-N 0.000 claims description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 2
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 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 claims description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001879 copper Chemical class 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 5
- YXGZTNUNHBXFAX-UHFFFAOYSA-N copper;1,10-phenanthroline Chemical compound [Cu+2].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YXGZTNUNHBXFAX-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- MJAMCTLGWXIKOT-UHFFFAOYSA-M benzyl-dimethyl-[2-[2-[2-methyl-4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]azanium;hydroxide Chemical compound [OH-].CC1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 MJAMCTLGWXIKOT-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229940099204 ritalin Drugs 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- MYXKPFMQWULLOH-UHFFFAOYSA-M tetramethylazanium;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].C[N+](C)(C)C MYXKPFMQWULLOH-UHFFFAOYSA-M 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种选择性地将二羟基-或多羟基醇转化成羰基化合物的方法,该方法中采用氧气(O2)作为氧化剂,在包含下列物质的催化体系的存在下进行:(1)铜盐、含有杂环配合体的铜盐或铜络合物盐,和(2)一种碱。
Description
本发明涉及一种选择性地将多羟基醇转化成相应的羰基化合物的催化氧化方法。
在包含(1)催化量的铜(I)盐;(2)二配位基配体如邻二氮杂菲配体;和(3)一种碱如碳酸盐的催化体系中将一级醇或二级醇氧化为羰基化合物的方法已经在美国专利文献US5912388中有所描述。但是该文献并未公开任何有关如何氧化多羟基醇的启示。
众所周知在二醇的需氧氧化反应中使用铜络合物会导致C-C键的断裂反应和/或导致过氧化反应而生成终产品碳酸(L.Prati,M-Rossi,J.Mol.Cat.,A:Chem.,1996,110,221;或K.K.Sen Gupta,B.N.Nandy,S.Sen Gupta,J.Chem.Res.1993,396)。
现在已经发现使用下面定义的催化体系可以避免C-C键的断裂。
本发明提供一种选择性地将二羟基一或多羟基醇转化成羰基化合物的方法,该方法中采用氧气(O2)作为氧化剂,在包含下列物质的催化体系的存在下进行:
(1)铜盐、含有杂环配体的铜盐或铜络合物盐,和
(2)一种碱。
二羟基-或多羟基醇适用于本发明。
二羟基醇的实例包括1,2-二醇如乙二醇、丙烷-1,2-二醇、丁烷-1,2-二醇;二醇如1,3-丙二醇、1,4-丁二醇、长链α,β-C5-C18烷二醇或α,ω-C5-C18烷基二醇如戊二醇、己二醇、辛二醇、十二烷二醇、二甘醇、三甘醇、环二醇如1,3-环戊二醇、1,2-、1,3-或1,4-环己二醇等。
多羟基醇的例子包括丙三醇、季戊四醇、山梨醇、糖、淀粉等。
铜盐选自CuCl、CuBr、CuI、CuNO3、CuBF4、CuSO4、CuPF6等,优选CuCl。
合适的配体最好为二配位基配体如1,10-邻二氮杂菲或取代的邻二氮杂菲如5-甲基-1,10-邻二氮杂菲、2,9-二甲基-1,10-邻二氮杂菲、4,7-二甲基-1,10-邻二氮杂菲、3,4,7,8-四甲基-1,10-邻二氮杂菲、4,7-二羟基-1,10-邻二氮杂菲、红菲绕啉、浴铜灵二磺酸盐、2,2’-联吡啶、2,2’-联吡啶基-3,3’-二羧酸盐、2,2’-二喹啉、双(2-吡啶基乙基)-胺、三(2-吡啶基乙基)胺、2-吡啶基-(N-叔丁基)-甲基亚胺、(2-吡啶基)甲醇、亚乙基(2,5-二羟基-苯基亚胺)或双(2-羟基-3,5-二叔丁基苯基)硫化物。其中优选邻二氮杂菲。
优选的铜络合物为碱金属盐[M4(Cu4OCl10)]或[M(CuCl3)]或[M2(CuCl4)]或它们的混合物,其中M为碱金属阳离子;铵盐[R1R2R3R4N]4(Cu4OCl10)或[R1R2R3R4N](CuCl3)或[R1R2R3R4N]2(CuCl4)或它们的混合物,其中R1-R4彼此独立地为C1-C6烷基、苯基或苄基。R1-R4相同的络合物的例子有[(CH3)4N]4(Cu4OCl10)或[(C2H5)4N]4(Cu4OCl10)等。R1-R4不相同的络合物也是合适的,例如苄基三乙基和苄基三甲基铵-铜络合物或苯基三乙基和苯基三甲基铵-铜络合物。
铜络合物的制备是已知的,已经由例如J.A.Bertrand和J.A.Kelley在文章Inorganic chemistry,8(9),(1969)1982中有所描述。
铜盐和配体形成络合物,如Cu2(μ2-Br)bipy2,衍生自2,2’-联吡啶与CuBr的反应;或[Cu(phen)2]+CuCl2 -,衍生自邻二氮杂菲如1,10-邻二氮杂菲与CuCl的反应。
醇与铜盐的摩尔比范围为1∶(0.01-0.1)。
碱可以是氢氧化物、氧化物或碳酸盐,例如LiOH、NaHCO3、Na2CO3、NaOH、K2CO3、KOH、MgO、CaCO3、Ca(OH)2、BaCO3、Al2O3(碱性的);季铵盐或其水合物,例如[R1R2R3R4N](OH)、[R1R2R3R4N](Hal),其中Hal为卤素、R1-R4如上所述;醇盐例如Na(OR5)、K(OR5),其中R5是C1-C6烷基,如甲基、乙基或叔丁基;选自安珀莱特树脂、ambersep、海泡石、水滑石或膨润土的非均相碱性载体。
烷基可以是直链的或支链的,Hal是氟、氯、溴或碘,优选氯。
碱的用量取决于所使用的碱。用季铵盐作为碱时铜盐与碱的摩尔比例如约为1∶2。
在本发明的一个具体实施方案中使用季铵盐或其水合物,优选四甲基氢氧化铵作为碱。所述的体系比用例如K2CO3作为碱的体系表现出更高的催化活性,并且碱的用量也有所降低。
本发明的方法优选在溶剂的存在下进行。
合适的溶剂包括芳族溶剂(如苯、甲苯、对二甲苯、氟苯、全氟代苯、异丁基苯、或1,3,5-三甲基苯),腈(如乙腈),烃类溶剂(如石油馏分),卤化溶剂(如二氯甲烷、四氯乙烯或1,2-二氯乙烷)或酯(如醋酸甲酯或醋酸乙酯)。优选的溶剂为甲苯和乙腈。
本发明的方法优选在升温的情况下进行,例如温度范围在30-140℃,特别是60-110℃,优选70-90℃。
本发明的方法可在大气压或升高的压力下进行,优选在大气压力下进行。
氧气可以以纯氧或空气的形式提供。将氧气或空气的气流缓慢地通过非均相反应混合物。
反应时间根据所使用的碱的不同在30分钟至2小时之间变化。
催化剂可以通过过滤和与季铵盐氢氧化物或醇钾的再反应而很容易地被循环使用。
如果需要,可以加入还原剂,还原剂例如选自Zn、肼、SO2、Na2S2O4。
下面将更详细的解释本发明。
实施例1
使用CuCl/phen/K2CO3进行1-(羟基-苯基甲基)环己醇的催化需氧氧化
在100ml的带有氧气进口和回流冷凝管的二颈圆底烧瓶中,将CuCl(22.5mg,0.24mmol)和1,10-邻二氮杂菲(43.6mg,0.24mmol)悬浮在20ml的甲苯中。将该混合物在室温下搅拌10-20分钟,然后连续地加入K2CO3(1.33g,9.68mmol)和二醇(4.84mmol)。在搅拌下将氧气缓慢的通过该混合物的同时将混合物在油浴中在大约70-90℃下加热30分钟。过滤后用气相色谱与质谱联用(GC/MS)来测定其转化率。在1小时内反应的转化率达到约在90%。作为替换也可使用乙腈作为溶剂。所得的翻转频率(TOF)为约20h-1。
实施例2
使用CuCl/phen/Me4N(OH)·5H2O进行1-(羟基-苯基甲基)环己醇的催化需氧氧化
在100ml的带有气体进口和回流冷凝管的二颈圆底烧瓶中加入CuCl(22.5mg,0.24mmol)、1,10-邻二氮杂菲(43.6mg,0.24mmol)和20ml干燥的甲苯(作为替换可使用乙腈)。将混合物在室温下搅拌10-20分钟,随后加入Me4N(OH)·5H2O(87.7mg,0.48mmol)。将非均相反应混合物搅拌5分钟后加入二醇(4.84mmol)。将该混合物在油浴中加热至大约70℃保持30分钟,并将氧气缓慢地通过该反应混合物,过滤后用气相色谱与质谱联用(GC/MS)来测定其转化率。在反应半个小时内反应的转化率达到约90%(翻转频率(TOF)=40h-1)。
从以上可以看出,当使用四甲基氢氧化铵五水合物代替K2CO3时,可以提高催化体系的催化活性。不仅碱的用量可降低到约10mol%(使用K2CO3时为200%),而且反应时间更短(反应用时30分钟而不是60分钟),翻转频率(TOF)约为40h-1。
实施例3
使用CuCl/Me4N(OH)·5H2O进行1-(羟基-苯基甲基)环己醇的催化需氧氧化
在100ml的带有气体进口和回流冷凝管的二颈圆底烧瓶中将CuCl(22.5mg,0.24mmol)和2eq.0.48mmmol的Me4N(OH)·5H2O悬浮在20ml甲苯中。加入醇以后米白色的淤浆变成褐红色,在缓慢的氧气气流下将反应混合物加热至大约70℃保持30分钟。冷却至室温后将反应粗品的混合物用GC/MS来进行分析。用1-(羟基-苯基甲基)环己醇作底物,该反应大约有超过90%转化成羟基酮(无分裂产物)。
实施例4
使用Me4N(Cu4OCl10)/Me4N(OH)·5H2O作为催化剂进行1-(羟基-苯基甲基)环己醇的催化需氧氧化
将四甲基铵[六-μ2-氯-μ4-氧-四氯铜(II)酸盐(100mg,0.1mmol)悬浮在10ml乙腈中,加入痕量的辞粉后搅拌混合物约5分钟。然后加入Me4N(OH)·5H2O(200mg,1mmol)和2.5mmol的乙醇。将混合物加热30分钟到约80℃,由此固体变成深褐色和溶液呈微红色。将粗反应混合物用GC分析,70%转化成羟基酮(无分裂产物)。
实施例5
将下表所列的底物在需氧条件下进行氧化,使用实施例1或2中描述的催化体系。
实施例6
[Cu(phen)2]+CuCl2 -的制备
CuCl与1当量的1,10-邻二氮杂菲反应,形成一种深紫罗兰色的、几乎不溶于所有有机溶剂的粉末。从乙腈溶液中可以获得适合X-射线分析的单晶。CuCl/phen的结构包括离子对[Cu(phen)2]+CuCl2 -,其在以前的文献中没有描述过。在拉曼光谱中可以观察到在308.6cm-1的Cu-Cl的伸缩振动。由于[Cu(phen)2]+CuCl2 -是一个稳定的化合物,这种络合物优选用于需氧氧化实验中。
Claims (5)
1.一种选择性地将二羟基-或多羟基醇转化成羰基化合物的方法,该方法中采用氧气(O2)作为氧化剂,在包含下列物质的催化体系的存在下进行:
(1)铜盐、含有杂环配体的铜盐或铜络合物盐,和
(2)一种碱。
2.如权利要求1所述的方法,其中
铜盐选自CuCl、CuBr、CuI、CuNO3、CuBF4、CuSO4、CuPF6;
配体选自1,10-邻二氮杂菲,5-甲基-1,10-邻二氮杂菲、2,9-二甲基-1,10-邻二氮杂菲、4,7-二甲基-1,10-邻二氮杂菲、3,4,7,8-四甲基-1,10-邻二氮杂菲、4,7-二羟基-1,10-邻二氮杂菲、红菲绕啉、浴铜灵二磺酸盐、2,2’-联吡啶、2,2’-联吡啶基-3,3’-二羧酸盐、2,2’-二喹啉、双(2-吡啶基乙基)-胺、三(2-吡啶基乙基)胺、2-吡啶基-(N-叔丁基)-甲基亚胺、(2-吡啶基)甲醇、亚乙基(2,5-二羟基-苯基亚胺)或双(2-羟基-3,5-二叔丁基苯基)硫化物;
铜络合物盐是[M4(Cu4OCl10)]或[M(CuCl3)]或[M2(CuCl4)]或它们的混合物,其中M为碱金属阳离子,[R1R2R3R4N]4(Cu4OCl10)或[R1R2R3R4N](CuCl3)或[R1R2R3R4N]2(CuCl4)或它们的混合物,其中R1-R4彼此独立地为C1-C6烷基、苯基或苄基;
碱选自LiOH、NaHCO3、Na2CO3、NaOH、K2CO3、KOH、MgO、CaCO3、Ca(OH)2、BaCO3、Al2O3(碱性的);季铵盐或其水合物,[R1R2R3R4N](OH)、[R1R2R3R4N](Hal),其中Hal为卤素,和R1-R4如上所述;醇盐Na(OR5)、K(OR5),其中R5是C1-C6烷基;或选自安珀莱特树脂、ambersep、海泡石、水滑石或膨润土的非均相碱性载体。
3.如权利要求1或2所述的方法,其中的铜盐是CuCl;配体是邻二氮杂菲配体;铜络合物是[R1R2R3R4N](Cu4OCl10);和碱是季铵盐或其水合物。
4.如权利要求1-3中任何一项所述的方法,其中的催化体系是CuCl/l,10-邻二氮杂菲/[(CH3)4N]OH·5H2O或CuCl/[(CH3)4N]OH·5H2O。
5.如权利要求1-4中任何一项所述的方法,其中该方法在溶剂存在下,在30-140℃的温度下进行。
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CN102348670A (zh) * | 2009-03-12 | 2012-02-08 | 吉坤日矿日石能源株式会社 | 羰基化合物的制造方法、催化剂及其制造方法 |
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WO2013085918A1 (en) * | 2011-12-05 | 2013-06-13 | The Regents Of The University Of California | Methods and compostions for generating polynucleic acid fragments |
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WO1997003033A1 (en) * | 1995-07-11 | 1997-01-30 | Zeneca Limited | Preparation of aldehydes or ketones from alcohols |
ATE240285T1 (de) * | 1999-11-19 | 2003-05-15 | Ciba Sc Holding Ag | Verfahren zur selektiven oxidation von alkoholen unter verwendung leicht abtrennbarer nitroxylradikale |
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CN106596775A (zh) * | 2016-12-19 | 2017-04-26 | 广电计量检测(成都)有限公司 | 塑料中十四氢化‑1,4a‑二甲基‑7‑(1‑甲基乙基)‑1‑菲甲醇的检测方法 |
CN106596775B (zh) * | 2016-12-19 | 2019-06-07 | 广电计量检测(成都)有限公司 | 塑料中十四氢化-1,4a-二甲基-7-(1-甲基乙基)-1-菲甲醇的检测方法 |
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WO2003084911A1 (en) | 2003-10-16 |
US20050203315A1 (en) | 2005-09-15 |
BR0309023A (pt) | 2005-02-01 |
EP1492753A1 (en) | 2005-01-05 |
AU2003240753A1 (en) | 2003-10-20 |
MXPA04009693A (es) | 2005-01-11 |
JP2005521740A (ja) | 2005-07-21 |
CA2480788A1 (en) | 2003-10-16 |
KR20040102069A (ko) | 2004-12-03 |
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