CN102336619A - 一种氧气氧化醇制备醛或酮的方法 - Google Patents
一种氧气氧化醇制备醛或酮的方法 Download PDFInfo
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- CN102336619A CN102336619A CN2010102371703A CN201010237170A CN102336619A CN 102336619 A CN102336619 A CN 102336619A CN 2010102371703 A CN2010102371703 A CN 2010102371703A CN 201010237170 A CN201010237170 A CN 201010237170A CN 102336619 A CN102336619 A CN 102336619A
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- Prior art keywords
- alcohol
- phenyl
- aldehydes
- aryl
- alkyl
- 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.)
- Granted
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000002576 ketones Chemical class 0.000 title claims abstract description 25
- 150000001299 aldehydes Chemical class 0.000 title claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000001301 oxygen Substances 0.000 title claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 title abstract description 3
- 230000035484 reaction time Effects 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 14
- -1 halogenophenyl Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims description 11
- 235000014121 butter Nutrition 0.000 claims description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 125000006501 nitrophenyl group Chemical group 0.000 claims description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 4
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical group [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 2
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 claims description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 229940102127 rubidium chloride Drugs 0.000 claims description 2
- 125000004426 substituted alkynyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 abstract 4
- 229910001504 inorganic chloride Inorganic materials 0.000 abstract 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 abstract 2
- AKKLAJYCGVIWBS-UHFFFAOYSA-N O=[N].CC1(C)CCCC(C)(C)N1 Chemical compound O=[N].CC1(C)CCCC(C)(C)N1 AKKLAJYCGVIWBS-UHFFFAOYSA-N 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 230000002194 synthesizing effect Effects 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- BVQVLAIMHVDZEL-UHFFFAOYSA-N 1-phenyl-1,2-propanedione Chemical compound CC(=O)C(=O)C1=CC=CC=C1 BVQVLAIMHVDZEL-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- NIOYUNMRJMEDGI-UHFFFAOYSA-N hexadecanal Chemical compound CCCCCCCCCCCCCCCC=O NIOYUNMRJMEDGI-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 2
- IDASOVSVRKONFS-UHFFFAOYSA-N 3-phenylprop-2-ynal Chemical compound O=CC#CC1=CC=CC=C1 IDASOVSVRKONFS-UHFFFAOYSA-N 0.000 description 2
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 2
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 2
- 235000014493 Crataegus Nutrition 0.000 description 2
- 241001092040 Crataegus Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- IJNJLGFTSIAHEA-UHFFFAOYSA-N prop-2-ynal Chemical compound O=CC#C IJNJLGFTSIAHEA-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- SSZZWKMSCLLYGN-UHFFFAOYSA-N 2-phenylcyclohex-2-en-1-ol Chemical compound OC1CCCC=C1C1=CC=CC=C1 SSZZWKMSCLLYGN-UHFFFAOYSA-N 0.000 description 1
- OSXVGKNAOBLNIW-UHFFFAOYSA-N 3-(4-nitrophenyl)prop-1-yn-1-ol Chemical compound [N+](=O)([O-])C1=CC=C(C=C1)CC#CO OSXVGKNAOBLNIW-UHFFFAOYSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- KDIAMAVWIJYWHN-UHFFFAOYSA-N CCCC1CCCC1 Chemical compound CCCC1CCCC1 KDIAMAVWIJYWHN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AMSFEMSYKQQCHL-UHFFFAOYSA-N hept-2-yne Chemical compound CCCCC#CC AMSFEMSYKQQCHL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XUZLXCQFXTZASF-UHFFFAOYSA-N nitro(phenyl)methanol Chemical compound [O-][N+](=O)C(O)C1=CC=CC=C1 XUZLXCQFXTZASF-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- MNZVNPXBJGMTLY-UHFFFAOYSA-N octa-5,7-dien-3-ol Chemical compound CCC(O)CC=CC=C MNZVNPXBJGMTLY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FWLKYEAOOIPJRL-UHFFFAOYSA-N prop-1-yn-1-ol Chemical compound CC#CO FWLKYEAOOIPJRL-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C45/38—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 primary 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
- B01J31/006—Catalysts comprising hydrides, coordination complexes or organic compounds comprising organic radicals, e.g. TEMPO
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供一种氧气氧化醇制备醛或酮的方法,系在室温下,在有机溶剂中,以硝酸铁(Fe(NO3)3·9H2O)、2,2,6,6-四甲基哌啶氮氧化物(TEMPO)和无机氯化物为催化剂,以氧气或空气作为氧化剂,反应时间为1-24小时,醇氧化生成醛或酮;其中,所述醇、2,2,6,6-四甲基哌啶氮氧化物、硝酸铁、无机氯化物的摩尔比为100∶1~10∶1~10∶1~10。本发明具有产率高、反应条件温和、操作简单、分离纯化方便、溶剂可回收、底物普适性广、整个过程对环境友好,不存在污染等诸多优点,是一种适合工业化生产的方法。
Description
技术领域
本发明涉及一种氧气氧化醇生产醛或酮的方法,具体涉及一种以铁催化的,通过氧气氧化醇制备醛或酮的方法。
背景技术
醛和酮是一类重要的精细化工原料,广泛应用于化学品的生产和研发等领域。氧化反应是一种基本的、重要的化学反应类型,工业上,醛和酮的生产主要通过氧化的方法获得。因此,寻找一种价格低廉、条件温和、环境友好、高效的催化氧化体系具有良好的应用前景。传统上,醛和酮的合成是通过利用至少是当量的氧化剂来氧化相应的醇而获得,这种方法虽然可以达到合成醛酮的目的,但由于使用氧化剂,如氧化铬、氧化锰、氧化钌等,以致反应过程产生对环境有害的从氧化剂衍生的副产物,因此,并不适用于大规模的工业生产(Chromium Oxidationsin Organic Chemistry;Springer:Berlin,1984;Regen,S.L.;Koteel,C.J.Am.Chem.Soc.1977,99,3837-3838;Griffith,W.P.Chem.Soc.Rev.1992,21,179-185)。因此,人们较为关注以氧气为氧化剂,通过过渡金属如Pd、Ru、Mo-Co、Co、Pt、Os-Cu、Os、Ni、Cu、Fe等催化氧化一级或二级醇生成相应的醛和酮的合成方法(Blackburn,T.F.;Schwartz,J.J.Chem.Soc.Chem.Commun.1977,157-158;Piera,J.;J.-E.Angew.Chem.Int.Ed.2008,47,3506;Sheldon,R.A.;Arends,I.W.C.E.;Brink,G.-J.T.;Dijksman,A.Acc.Chem.Res.2002,35,774;Mallat,T.;Baiker,A.Chem.Rev.2004,104,3037)。TEMPO作为一种稳定的氧自由基,在与Fe或者Cu协同催化氧化一级或二级醇生成相应的醛或酮的过程中发挥了重要的作用。
本发明克服了现有技术中使用重金属作为催化剂、反应条件比较苛刻、反应时间较长、催化底物类型有局限、反应温度高、使用高压等缺陷,提供了一种通过一大气压氧气氧化来生成醛或酮的方法,以硝酸铁、TEMPO、无机氯化物作为共催化剂,以氧气作为氧化剂,减少化学反应的废弃物和污染,降低成本,原料来源广泛,具有反应温和、高效、适用大规模生产、低成本、环保等有益效果。
发明内容
本发明的目的在于提供一种反应条件温和、高效、低成本、绿色的催化氧气氧化醇制备醛或酮的方法。
本发明提供的一种氧气氧化醇制备醛或酮的方法,其特征在于,在室温下,在有机溶剂中,以氧气或空气作为氧化剂,以硝酸铁、2,2,6,6-四甲基哌啶氮氧化物(TEMPO)、无机氯化物作为催化剂,反应时间为1-24小时,醇氧化生成醛或酮;其中,所述醇、2,2,6,6-四甲基哌啶氮氧化物、硝酸铁、无机氯化物的摩尔比为100∶1~10∶1~10∶1~10。
本发明所述醇是R1R2CHOH,或C5-C8环醇;其中,醇R1R2CHOH的分子式中,所述R1是氢、C1-16的烷基、R3和/或R4取代的烯基、R5和/或R6取代的联烯基、R7取代的炔基、芳基、三氟甲基苯基、硝基苯基、卤代苯基、或C1-4的烷氧基苯基;所述R2是氢、C1-16的烷基、芳基、三氟甲基苯基、卤代苯基或甲氧基苯基;其中,所述R3是C1-C6的烷基或芳基;所述R4是氢、C1-C6的烷基或芳基;所述R5是氢、C1-9的烷基、芳苯基或苄基;所述R6是氢、C4-C9的烷基、芳基或苄基;所述R7是氢、C1-12的烷基、三甲基硅基、芳基、卤代苯基、硝基苯基或甲氧基苯基。所述芳基为苯基、卤代苯基、烷氧基苯基或萘基。
本发明所述C5-C8环醇可以是环戊醇、环己醇、环庚醇、或环辛醇。
本发明所述有机溶剂为苯、甲苯、二氯甲烷、二氯乙烷、1,2-二氯乙烷、1,1-二氯乙烷、1,2-二氯丙烷、1,3-二氯丙烷、硝基甲烷、乙二醇二甲醚、四氢呋喃、乙腈或乙酸乙酯中的一种或多种混合。
本发明无机氯化物为氯化钠、氯化钾、氯化锂、氯化铷、氯化铯。优选为氯化钠。
本发明醇、2,2,6,6-四甲基哌啶氮氧化物、硝酸铁、无机氯化物的优选的摩尔比为100∶5∶10∶10。
本发明公开了在室温下,在有机溶剂中,以Fe(NO3)3.9H2O、TEMPO(2,2,6,6-四甲基哌啶氮氧化物)、和无机氯化物(NaCl)为催化剂,以氧气作为氧化剂,氧化醇生成相应的醛酮的方法。本发明的方法,通过常压下空气中的氧气或纯氧气,可以将含有碳碳单键,碳碳双键,碳碳三键等官能团的醇选择性地氧化,将一级醇或者二级醇氧化生成相应的醛及酮。本发明具有产率高、反应条件温和、操作简单、分离纯化方便、溶剂可回收、底物普适性广、整个过程对环境友好,不存在污染等诸多优点,是一种适合工业化生产的方法。
本发明具有底物普适性广的优点,以Fe、TEMPO和无机氯化物为共催化剂,既可催化氧化普通醇、苄醇、烯醇和环醇等,又可用于催化氧化结构比较复杂的醇,如炔丙醇、联烯醇等。本发明反应条件温和、操作简单、分离纯化方便、溶剂可回收等优点,本发明方法的产率高,催化效率高,比如,催化剂的用量低至1mol%时就能产生有效反应。本发明克服了现有技术中使用重金属作为催化剂、反应条件比较苛刻、反应时间较长、催化底物类型有局限等缺陷。本发明的方法,既适用于小规模的实验室合成,也适用于大规模的工业生产。
本发明采用便宜、来源广泛且丰富的氧气或空气作为氧化剂,替代传统氧化剂体系中所使用的化学氧化剂。由于本发明催化氧化条件极为温和,因此,只需在室温、常压、中性的条件下就可以进行,操作极为便利且易于控制。在室温下,比如在1个大气压的氧气压力下,反应就可以顺利进行。由于反应过程中所用氧化剂是氧气,副产物是水,因此,整个反应过程几乎对环境不会造成任何污染,是一种绿色化学合成方法。本发明后处理简单,产品收率高,有效降低了生产制造成本。
具体实施方式
以下实施例有助于理解本发明,但不限于本发明的内容。
实施例1:2-苄基-2,3-丁二烯醛的合成
其中,atm为大气压;balloon为气球;rt为室温。
将Fe(NO3)3·9H2O(20.3mg,0.05mmol),1,2-二氯乙烷(DCE,4mL),2,2,6,6-四甲基哌啶氮氧化物(TEMPO,15.6mg,0.10mmol)和NaCl(5.8mg,0.10mmol)加入到10mL三口瓶中。在氧气氛围下,室温搅拌5min.将2-苄基-2,3-丁二烯醇(160.6mg,1.0mmol)溶于DCE(1mL)中,滴加到反应液中,TLC监测直至反应完成。反应液以乙醚(30mL)稀释,无水MgSO4干燥,垫层硅胶过滤,浓缩得粗产品。该粗产品通过硅胶柱层析(石油醚∶乙酸乙酯=20∶1)得到相应的2-苄基-2,3-丁二烯醛(114.5mg,72%)。1H NMR(300MHz,CDCl3)δ9.61(s,1H),7.31-7.15(m,5H),5.28(t,J=2.4Hz,2H),3.52(t,J=2.6Hz,2H);13C NMR(75.4MHz,CDCl3)δ222.50,191.41,138.52,128.84,128.35,126.41,110.62,80.83,30.84;IR(neat)2827,2728,1955,1928,1677,1602,1495,1454,1426,1227,1144,1071,1030cm-1;MS(EI)m/z 158(M+,5.25),129(100);HRMS计算值C11H10O(M+):158.0732;实测值:158.07333.
实施例2:2,3-十三烷基二烯醛的合成
其他操作参考实施例1,所用原料为2,3-十三烷基二烯醇,反应时间为5小时,得到2,3-十三烷基二烯醛,总产率为80%。1H NMR(300MHz,CDCl3)δ9.44(d,J=7.2Hz,1H),5.84-5.71(m,2H),2.25-2.10(m,2H),1.55-1.42(m,2H),1.42-1.20(m,12H),0.84(t,J=6.6Hz,3H);13C NMR(75.4MHz,CDCl3)δ218.94,192.00,98.47,96.19,31.73,29.38,29.17,29.15,28.82,28.71,27.36,22.53,13.94;MS(EI)m/z 194(M+,0.79),81(100);IR(neat)2924,2854,1943,1690,1465,1107,1081cm-1;HRMS计算值C13H22O(M+):194.1671;实测值:194.1671.
实施例3:1,2-十三烷基二烯-4-酮的合成
其他操作参考实施例1,所用原料为1,2-十三烷基二烯-4-醇(196.2mg,1.0mmol),反应时间为10.5小时,得到1,2-十三烷基二烯-4-酮(161.7mg,84%)。1H NMR(300MHz,CDCl3)δ5.74(t,J=6.5Hz,1H),5.20(d,J=6.3Hz,2H),2.57(t,J=7.4Hz,2H),1.63-1.50(m,2H),1.35-1.17(m,12H),0.85(t,J=6.3Hz,3H);13C NMR(75.4MHz,CDCl3)δ216.57,200.88,96.62,79.16,39.19,31.81,29.37,29.33,29.19,29.14,24.53,22.59,14.00;IR(neat)2955,2854,1961,1934,1681,1465,1410,1365,1157,1105,1068cm-1;MS(EI)m/z 194(M+,1.37),41(100);HRMS计算值C13H22O(M+):194.1671;实测值:194.1673.
实施例4:2-己基-1-苯基2,3-丁二烯酮的合成
其他操作参考实施例1,所用原料为2-己基-1-苯基2,3-丁二烯醇(229.4mg,1.0mmol),反应时间为23小时,得到2-己基-1-苯基2,3-丁二烯酮(123.1mg,54%)。1H NMR(300MHz,CDCl3)δ7.76(d,J=7.8Hz,2H),7.49(t,J=7.1Hz,1H),7.38(t,J=7.7Hz,2H),5.04(t,J=2.7Hz,2H),2.45-2.35(m,2H),1.58-1.25(m,8H),0.90(t,J=6.5Hz,3H);13C NMR(75.4MHz,CDCl3)δ216.95,194.78,138.34,131.85,128.97,127.73,106.88,79.26,31.56,28.85,27.83,27.80,22.53,13.98;IR(neat)3059,2955,2856,1932,1650,1598,1579,1447,1315,1269,1177,1072cm-1;MS(EI)m/z 228(M+,1.69),105(100);HRMS计算值C16H20O(M+):228.1514;实测值:228.1512.
实施例5:1-对氯苯基-2,3-丁二烯酮的合成
其他操作参考实施例1,所用原料为1-对氯苯基-2,3-丁二烯醇(180.1mg,1.0mmol),反应时间为4小时,得到1-对氯苯基-2,3-丁二烯酮(unstable upon evaporation,NMR yield 84%)。1H NMR(300MHz,CDCl3)δ7.83(d,J=8.1Hz,2H),7.41(d,J=7.8Hz,2H),6.38(t,J=6.5Hz,1H),5.26(d,J=6.3Hz,2H);13C NMR(75.4MHz,CDCl3)δ216.38,188.88,138.41,134.99,129.38,127.95,92.46,78.76;IR(neat):1961,1931,1652,1588,1277,1212,1091cm-1;MS(EI)m/z180(M(37Cl)+,2.53),178(M(35Cl)+,10.29),139(100);HRMS计算值C10H7 35ClO(M+):178.0185;实测值:178.0185.
实施例6:3-己基-1,2-辛二烯-4-酮的合成
其他操作参考实施例1,所用原料为3-己基-1,2-辛二烯-4-醇(211.3mg,1.0mmol),反应时间为4小时,得到3-己基-1,2-辛二烯-4-酮(156.1mg,75%)。1H NMR(300MHz,CDCl3)δ5.16(t,J=2.9Hz,2H),2.64(t,J=7.7Hz,2H),2.20-2.10(m,2H),1.61-1.49(m,2H),1.42-1.21(m,10H),0.93-0.82(m,6H);13C NMR(75.4MHz,CDCl3)δ216.25,201.38,108.62,79.35,38.94,31.61,28.88,27.82,27.21,26.27,22.58,22.37,14.02,13.82;IR(neat):2957,2928,2858,1934,1677,1464,1410,1379,1349,1259,1175,1086,1020cm-1;MS(EI)m/z 208(M+,0.48),85(100);HRMS计算值C14H24O(M+):208.1827;实测值:208.1826.
实施例7:2-壬炔醛的合成
其他操作参考实施例1,所用原料为2-壬炔醇(140.1mg,1.0mmol),反应时间为3小时,得到2-壬炔醛(119.9mg,87%)。1H NMR(300MHz,CDCl3)δ9.18(s,1H),2.41(t,J=7.1Hz,2H),1.66-1.50(m,2H),1.48-1.24(m,6H),0.90(t,J=6.6Hz,3H);13C NMR(75.4MHz,CDCl3)δ176.86,99.20,81.61,31.07,28.39,27.41,22.34,19.00,13.86;IR(neat)2930,2859,2237,2200,1716,1670,1458,1380,1278,1225,1137cm-1;MS(EI)m/z 138(M+,0.40),137(M+-H,1.57),41(100).
实施例8:3-苯基丙炔醛的合成
其他操作参考实施例1,所用原料为3-苯基丙炔醇(132.0mg,1.0mmol),反应时间为2.3小时,得到3-苯基丙炔醛(111.9mg,86%)。1H NMR(300MHz,CDCl3)δ9.41(s,1H),7.59(d,J=7.8Hz,2H),7.48(t,J=6.9Hz,1H),7.39(t,J=6.9Hz,2H);13C NMR(75.4MHz,CDCl3)δ176.61,133.16,131.19,128.65,119.34,94.96,88.35;IR(neat)2854,2738,2240,2185,1654,1489,1443,1387,1260,1070cm-1;MS(EI)m/z 130(M+,64.02),102(100).
实施例9:3-对硝基苯基炔丙醛的合成
其他操作参考实施例1,所用原料为3-对硝基苯基炔丙醇(177.5mg,1.0mmol),反应时间为1.7小时,得到3-对硝基苯基炔丙醛(125.5mg,72%)。1H NMR(300MHz,CDCl3)δ9.43(s,1H),8.24(d,J=8.4Hz,2H),7.75(d,J=8.7Hz,2H);13C NMR(75.4MHz,CDCl3)δ176.03,148.70,133.78,125.87,123.71,90.67,90.49;IR(neat)2924,2854,2195,1655,1592,1511,1342,1103cm-1.
实施例10:3-对甲氧基苯炔丙醛的合成
其他操作参考实施例1,所用原料为3-对甲氧基苯炔丙醇(161.9mg,1.0mmol),反应时间为3.5小时,得到3-对甲氧基苯炔丙醛(110.8mg,69%)。1H NMR(300MHz,CDCl3)δ9.38(s,1H),7.54(d,J=8.7Hz,2H),6.90(d,J=8.7Hz,2H),3.83(s,3H);13C NMR(75.4MHz,CDCl3)δ176.32,161.78,135.03,114.14,110.67,96.15,88.37,55.07;IR(neat)2178,1643,1598,1507,1303,1254,1175,1022cm-1;MS(EI)m/z(%)160(M+,100).
实施例11:1-对三氟甲基苯基-2-己炔酮的合成
其他操作参考实施例1,所用原料为1-对三氟甲基苯基-2-己炔醇(256.3mg,1.0mmol),反应时间为3小时,得到1-对三氟甲基苯基-2-己炔酮(201.0mg,79%)。1H NMR(300MHz,CDCl3)δ8.24(d,J=8.1Hz,2H),7.74(d,J=8.1Hz,2H),2.54(t,J=6.9Hz,2H),1.75-1.61(m,2H),1.58-1.44(m,2H),0.98(t,J=7.4Hz,3H);13C NMR(75.4MHz,CDCl3)δ176.78,139.45,134.91(q,J=32.3Hz),129.70,125.60-125.40(m),123.54(q,J=272.6Hz),98.27,79.38,29.70,22.02,18.85,13.37;IR(neat)2962,2936,2875,2239,2201,1650,1583,1509,1466,1411,1322,1261,1170,1128,1108,1064,1016cm-1;MS(EI)m/z 254(M+,3.14),173(100);HRMS计算值C14H13OF3(M+):254.0918;实测值:254.0919.
实施例12:1-苯基庚炔-3-酮的合成
其他操作参考实施例1,所用原料为1-苯基庚炔-3-醇(187.8mg,1.0mmol),反应时间为2.5小时,得到1-苯基庚炔-3-酮(161.3mg,87%)。1H NMR(300MHz,CDCl3)δ7.56(d,J=7.5Hz,2H),7.47-7.30(m,3H),2.66(t,J=7.4Hz,2H),1.78-1.64(m,2H),1.46-1.31(m,2H),0.95(t,J=7.4Hz,3H);13C NMR(75.4MHz,CDCl3)δ188.01,132.87,130.50,128.50,119.97,90.37,87.77,45.14,26.14,22.05,13.70;IR(neat)3063,2958,2872,2201,1666,1489,1443,1272,1158,1125,1067cm-1;MS(EI)m/z 186(M+,1.67),129(100).
实施例13:1-叔丁基二甲基硅氧基-2-十一烷基炔-4-酮的合成
其他操作参考实施例1,所用原料为1-叔丁基二甲基硅氧基-2-十一烷基炔-4-醇(21-97.5mg,1.0mmol),反应时间为3.5小时,得到1-叔丁基二甲基硅氧基-2-十一烷基炔-4-酮(267.1mg,90%)。1H NMR(300MHz,CDCl3)δ4.46(s,2H),2.54(t,J=7.4Hz,2H),1.74-1.62(m,2H),1.38-1.22(m,8H),0.96-0.86(m,12H),0.13(s,6H);13C NMR(75.4MHz,CDCl3)δ187.71,90.19,83.88,51.50,45.33,31.59,28.95,28.90,25.70,23.97,22.55,18.22,14.0,-5.23;IR(neat)2929,2857,2216,1679,1464,1364,1255,1153,1098cm-1;MS(EI)m/z 296(M+,0.15),239(M+-But,67.49),75(100);HRMS计算值C17H32O2Si(M+):296.2172;实测值:296.2174.
实施例14:1-苯基-3-三甲基硅基-2丙炔酮的合成
其他操作参考实施例1,所用原料为1-苯基-3-三甲基硅基-2丙炔醇(204.9mg,1.0mmol),反应时间为1.5小时,得到1-苯基-3-三甲基硅基-2丙炔酮(191.0mg,94%)。1H NMR(300MHz,CDCl3)δ8.14(d,J=8.1Hz,2H),7.61(t,J=7.4Hz,1H),7.48(t,J=7.7Hz,2H),0.32(s,9H);13C NMR(75.4MHz,CDCl3)δ177.64,136.48,134.11,129.60,128.54,100.84,100.49,-0.73;IR(neat)2153,1643,1598,1579,1450,1312,1243,1173,1035,1016cm-1;MS(EI)m/z 202(M+,16.37),187(100).
实施例15:1-对甲氧基苯基-2-庚炔酮的合成
其他操作参考实施例1,所用原料为1-对甲氧基苯基-2-庚炔醇(218.7mg,1.0mmol),反应时间为3小时,得到1-对甲氧基苯基-2-庚炔酮(195.0mg,90%)。1H NMR(300MHz,CDCl3)δ8.10(d,J=8.4Hz,2H),6.94(d,J=8.7Hz,2H),3.87(s,3H),2.48(t,J=6.9Hz,2H),1.71-1.58(m,2H),1.57-1.42(m,2H),0.96(t,J=7.2Hz,3H);13C NMR(75.4MHz,CDCl3)δ176.74,164.12,131.70,130.23,113.57,95.69,79.50,55.38,29.76,21.91,18.71,13.35;IR(neat)2958,2934,2872,2238,2199,1635,1594,1573,1508,1460,1421,1316,1251,1164,1113,1026cm-1;MS(EI)m/z 216(M+,63.27),135(100).
实施例16:6-圭炔-5-酮的合成
其他操作参考实施例1,所用原料为6-圭炔-5-醇(168.4mg,1.0mmol),反应时间为4小时,得到6-圭炔-5-酮(151.8mg,91%)。1H NMR(300MHz,CDCl3)δ2.52(t,J=7.4Hz,2H),2.37(t,J=6.9Hz,2H),1.71-1.60(m,4H),1.60-1.28(m,4H),0.97-0.89(m,6H);13C NMR(75.4MHz,CDCl3)δ188.43,94.10,80.87,45.20,29.71,26.19,22.08,21.89,18.57,13.72,13.40;IR(neat)2959,2933,2873,2213,1672,1465,1243,1168cm-1;MS(EI)m/z 165(M+-H,0.07),151(M+CH3,4.57),109(M+-Bu-n,100).
实施例17:十二烷基炔-3-酮的合成
其他操作参考实施例1,所用原料为十二烷基炔-3-醇(182.2mg,1.0mmol),反应时间为5小时,得到十二烷基炔-3-酮(156.5mg,87%)。1H NMR(300MHz,CDCl3)δ3.20(s,1H),2.58(t,J=7.4Hz,2H),1.75-1.60(m,2H),1.37-1.20(m,12H),0.88(t,J=6.3Hz,3H);13C NMR(75.4MHz,CDCl3)δ187.51,81.49,78.18,45.44,31.82,29.33,29.26,29.20,28.87,23.77,22.63,14.04;IR(neat):2925,2855,2093,1681,1465,1404,1377,1205,1132,1089,1051cm-1;MS(EI)m/z 180(M+,0.22),179(M+-H,0.85),53(100).
实施例18:反式-3,7-二甲基-2,6-辛二烯醛的合成
其他操作参考实施例1,所用原料为反式-3,7-二甲基-2,6-辛二烯醇(154.7mg,1.0mmol),反应时间为8小时,得到反式-3,7-二甲基-2,6-辛二烯醛(141.3mg,93%)。1H NMR(300MHz,CDCl3)δ9.98(d,J=7.5Hz,1H),5.87(d,J=7.2Hz,1H),5.07(s,1H),2.30-2.10(m,7H),1.68(s,3H),1.61(s,3H);13C NMR(75.4MHz,CDCl3)δ191.18,163.70,132.82,127.34,122.52,40.52,25.67,25.54,17.60,17.47;IR(neat)2968,2917,2856,1671,1632,1611,1442,1379,1193,1120,1044cm-1;MS(EI)m/z(%)152(M+,2.55),69(100).
实施例19:反式-4-甲基-1-苯基戊烯-3-酮的合成
其他操作参考实施例1,所用原料为反式-4-甲基-1-苯基戊烯-3-醇(176.6mg,1.0mmol),反应时间为4小时,得到反式-4-甲基-1-苯基戊烯-3-酮(102.8mg,59%)。1H NMR(300MHz,CDCl3)δ7.61(d,J=16.2Hz,1H),7.57-7.52(m,2H),7.41-7.34(m,3H),6.82(d,J=7.8Hz,1H),2.93(hept,J=6.9Hz,1H),1.19(s,3H),1.17(s,3H);13C NMR(75.4MHz,CDCl3)δ203.62,142.27,134.59,130.21,128.79,128.16,124.36,39.14,18.37;IR(neat)3028,1687,1662,1610,1576,1495,1465,1449,1383,1348,1301,1201,1147,1120,1087,1054cm-1;MS(EI)m/z 159(M+-CH3,7.13),41(100).
实施例20:2-苯基-2-环己烯酮的合成
其他操作参考实施例1,所用原料为2-苯基-2-环己烯醇(175.0mg,1.0mmol),反应时间为4小时,得到2-苯基-2-环己烯酮(149.2mg,86%)。1H NMR(300MHz,CDCl3)δ7.34-7.20(m,5H),6.95(t,J=4.1Hz,1H),2.56-2.40(m,4H),2.08-1.96(m,2H);13C NMR(75.4MHz,CDCl3)δ197.47,147.75,139.92,136.32,128.31,127.61,127.16,38.73,26.22,22.57;IR(neat)2948,2930,1661,1553,1491,1443,1427,1357,1315,1279,1261,1208,1155,1119,1071,1032cm-1;MS(EI)m/z 172(M+,59.46),115(100).
实施例21:对氯苯甲醛的合成
其他操作参考实施例1,所用原料为对氯苄基醇(142.3mg,1.0mmol),反应时间为3小时,得到对氯苯甲醛(122.2mg,87%)。1H NMR(300MHz,CDCl3)δ9.98(s,1H),7.82(d,J=7.5Hz,2H),7.51(d,J=7.8Hz,2H);13C NMR(75.4MHz,CDCl3)δ190.75,140.91,134.72,130.85,129.42;IR(neat):2856,1699,1588,1575,1485,1385,1295,1264,1205,1165,1092,1012cm-1;MS(EI)m/z 142(M+(37Cl),10.04),140(M+(35Cl),35.62),41(100).
实施例22:对甲氧基苯甲醛的合成
其他操作参考实施例1,所用原料为对甲氧基苄基醇(137.8mg,1.0mmol),反应时间为3小时,得到对甲氧基苯甲醛(122.4mg,90%)。1H NMR(300MHz,CDCl3)δ9.87(s,1H),7.82(d,J=8.4Hz,2H),6.99(d,J=8.4Hz,2H),3.87(s,3H);13C NMR(75.4MHz,CDCl3)δ190.24,164.13,131.45,129.49,113.84,55.09;IR(neat)2840,2739,1680,1595,1576,1510,1460,1426,1393,1314,1255,1214,1182,1157,1108,1021cm-1;MS(EI)m/z 136(M+,69.21),135(100).
实施例23:对硝基苯甲醛的合
其他操作参考实施例1,所用原料为对硝基苄醇(153.1mg,1.0mmol),反应时间为2.5小时,得到对硝基苯甲醛(141.6mg,94%)。1HNMR(300MHz,CDCl3)δ10.16(s,1H),8.39(d,J=8.4Hz,2H),8.07(d,J=8.4Hz,2H);13C NMR(75.4MHz,CDCl3)δ190.23,140.07,130.45,124.28;IR(neat)2852,1707,1606,1539,1382,1346,1325,1287,1198,1105,1008cm-1;MS(EI)m/z 151(M+,73.95),51(100).
实施例24:乙酰苯基酮的合成
其他操作参考实施例1,所用原料为1-苯基乙醇(121.4mg,1.0mmol),反应时间为3小时,得到乙酰苯基酮(106.9mg,89%)。1H NMR(300MHz,CDCl3)δ7.96(d,J=7.8Hz,2H),7.56(t,J=7.4Hz,1H),7.46(t,J=7.7Hz,2H),2.60(s,3H);13C NMR(75.4MHz,CDCl3)δ198.09,137.15,133.05,128.54,128.27,26.53;IR(neat)1681,1598,1582,1448,1358,1263,1180,1078,1024cm-1;MS(EI)m/z 120(M+,33.35),77(100).
实施例25:十六烷基醛的合成
其他操作参考实施例1,所用原料为十六烷基醇(242.7mg,1.0mmol),反应时间为11小时,得到十六烷基醛(168.5mg,70%)。1H NMR(300MHz,CDCl3)δ9.76(s,1H),2.41(t,J=7.4Hz,2H),1.68-1.56(m,2H),1.36-1.18(m,24H),0.88(t,J=6.2Hz,3H);13C NMR(75.4MHz,CDCl3)δ202.82,43.89,31.91,29.64,29.56,29.40,29.33,29.16,22.66,22.08,14.06;IR(neat)2912,2849,1729,1704,1470,1411,1392,1373cm-1;MS(EI)m/z 240(M+,2.20),57(100).
实施例26:十三烷基-2-酮的合成
其他操作参考实施例1,所用原料为十三烷基-2-醇(201.1mg,1.0mmol),反应时间为7小时,得到十三烷基-2-酮(186.4mg,94%)。1H NMR(300MHz,CDCl3)δ2.31(t,J=7.4Hz,2H),2.02(s,3H),1.53-1.42(m,2H),1.27-1.10(m,16H),0.78(t,J=6.3Hz,3H);13C NMR(75.4MHz,CDCl3)δ208.60,43.52,31.71,29.47,29.42,29.29,29.22,29.14,28.99,23.66,22.47,13.84;IR(neat)2923,2853,1717,1465,1411,1358,1260,1226,1162cm-1;MS(EI)m/z 198(M+,2.18),43(100).
实施例27:环己酮的合成
将Fe(NO3)3·9H2O(2.0681g,5.0mmol),TEMPO(781.3mg,5.0mmol)和NaCl(299.0mg,5.0mmol)和DCE(50mL)加入到100mL三口瓶中。在氧气氛围下,室温搅拌5min.将环己醇(10.0718g,100.0mmol)滴加到反应液中,反应放热,保持温度不超过50℃,TLC监测直至反应完成。减压蒸馏(20mmHg,68-71℃)得产品环己酮(8.33g,85%).1H NMR(300MHz,CDCl3)δ2.33(t,J=6.6Hz,4H),1.90-1.80(m,4H),1.77-1.63(m,2H);13C NMR(75.4MHz,CDCl3)δ212.13,41.64,26.73,25.22.
实施例28:乙酰苯基酮的合成
将Fe(NO3)3·9H2O(16.1607g,40.0mmol),TEMPO(6.2510g,40.0mmol)和NaCl(2.3377g,40.0mmol)和DCE(400mL)加入到2L三口瓶中。在氧气氛围下,室温搅拌10min.将1-苯基乙醇(488.64g,4.0mol)滴加到反应液中,反应放热,保持温度不超过50℃,TLC监测直至反应完成。常压下将反应液中的溶剂DCE蒸出(350mL,回收率88%);减压下(b.p.98~100℃/20mmHg,)将产品乙酰苯基酮蒸出,得产品436.6414g,收率91%。
实施例29-34:
将Fe(NO3)3·9H2O(0.05mmol),1,2-二氯乙烷(DCE,4mL),TEMPO(0.05mmol)和Additive(0.05mmol)加入到10mL三口瓶中。在氧气氛围下,室温搅拌5min.将2-己基-1-苯基2,3-丁二烯醇(0.5mmol)溶于DCE(1mL)中,滴加到反应液中,TLC监测直至反应完成。反应液以乙醚(30mL)稀释,无水MgSO4干燥,垫层硅胶过滤,浓缩,加入均三甲苯(46uL),用核磁(1H NMR,300MHz)分析转化率和收率.
Claims (6)
1.一种氧气氧化醇制备醛或酮的方法,其特征在于,在室温下,在有机溶剂中,以氧气或空气作为氧化剂,以硝酸铁、2,2,6,6-四甲基哌啶氮氧化物、无机氯化物作为催化剂,反应时间为1-24小时,醇氧化生成醛或酮;其中,所述醇、2,2,6,6-四甲基哌啶氮氧化物、硝酸铁、无机氯化物的摩尔比为100∶1~10∶1~10∶1~10。
2.如权利要求1所述氧气氧化醇制备醛或酮的方法,其特征在于,所述醇是R1R2CHOH、或C5-C8环醇;
其中,所述R1是氢、C1-16的烷基、R3和/或R4取代的烯基、R5和/或R6取代的联烯基、R7取代的炔基、芳基、三氟甲基苯基、硝基苯基、卤代苯基、或C1-4的烷氧基苯基;所述R2是氢、C1-16的烷基、芳基、三氟甲基苯基、卤代苯基或甲氧基苯基;
其中,所述R3是C1-C6的烷基或芳基;所述R4是氢、C1-C6的烷基或芳基;所述R5是氢、C1-9的烷基、芳苯基或苄基;所述R6是氢、C4-C9的烷基、芳基或苄基;所述R7是氢、C1-12的烷基、三甲基硅基、芳基、卤代苯基、硝基苯基或甲氧基苯基。
3.如权利要求2所述氧气氧化醇制备醛或酮的方法,其特征在于,所述芳基为苯基、卤代苯基、烷氧基苯基或萘基。
4.如权利要求2所述氧气氧化醇制备醛或酮的方法,其特征在于,所述C5-C8环醇为环戊醇、环己醇、环庚醇、或环辛醇。
5.如权利要求1所述氧气氧化醇制备醛或酮的方法,其特征在于,所述有机溶剂为苯、甲苯、二氯甲烷、1,2-二氯乙烷、1,1-二氯乙烷、1,2-二氯丙烷、1,3-二氯丙烷、硝基甲烷、乙二醇二甲醚、四氢呋喃、乙腈或乙酸乙酯中的一种或多种混合。
6.如权利要求1所述氧气氧化醇制备醛或酮的方法,其特征在于,所述无机氯化物为氯化钠、氯化钾、氯化锂、氯化铷、或氯化铯。
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