以 2,6-二叔丁基-4-甲基苯酚(BHT)为自由基捕捉剂,研究了四(五氟化苯基)-六,七溴-卟啉氯化铁选择性催化氧化超临界丙烷为丙醇的反应机理. 结果表明,添加少量的BHT能促进反应进行,过量的BHT则抑制反应进行. 反应产物中除有丙基自由基外,还有异丙氧自由基及其他微量反应产物(如异己烷、正己烷、双丙基过氧化物)存在. 超临界丙烷在催化剂的作用下形成更多的丙基自由基,进一步证明金属卟啉催化氧化超临界丙烷是链式自由基自氧化反应机理. 对于其他微量反应产物如乙醇、乙酸和丙酸的存在,不能用链式自由基自氧化反应机理进行解释.
参考文献
[1] | Meunier B .[J].Chemical Reviews,1992,92(06):1411. |
[2] | Traylor P S;Dolphin D;Traylor T G.[J].Journal of the Chemical Society Chemical Communication,1984(05):279. |
[3] | Traylor T G;Tsuchiya S .[J].Inorganic Chemistry,1987,26(08):1338. |
[4] | Wijesekera T;Matsumoto A;Dolphin D;Lexa D .[J].Angewandte Chemie International Edition in English,1990,29(09):1028. |
[5] | Hoffmann P;Labat G;Robert A;Meunier B .[J].Tetrahedron Letters,1990,31(14):1991. |
[6] | Tsuchiya S;Seno M.[J].CHEMISTRY LETTERS,1989(02):263. |
[7] | Gross Z;Nimri S;Barzilay C M;Simkhovich L .[J].Journal of Biological Inorganic Chemistry,1997,2(04):492. |
[8] | Ellis P E Jr;Lyons J E.[J].Journal of the Chemical Society Chemical Communication,1989(17):1189. |
[9] | Ellis P E Jr;Lyons J E.[J].Journal of the Chemical Society Chemical Communication,1989(18):1315. |
[10] | Ellis P E Jr;Lyons J E .[J].Catalysis Letters,1989,3(5-6):389. |
[11] | Ellis P E Jr;Lyons J E.[J].Journal of the Chemical Society Chemical Communication,1989(17):1187. |
[12] | Grinstaff M W;Hill M G;Labinger J A;Gray H B .[J].Science,1994,264(5163):1311. |
[13] | Labinger J A .[J].Catalysis Letters,1994,26(1-2):95. |
[14] | 刘依农,李红旗,赵锁奇,王仁安.四(五氟化苯基)卟啉氯化铁选择催化氧化超临界丙烷的反应机理[J].催化学报,2003(07):543-548. |
[15] | 朱自强.超临界流体技术:原理和应用[M].北京:化学工业出版社,2000 |
[16] | Birnbaum E R;Le Lacheur R M;Horton A C;Tumas W .[J].Journal of Molecular Catalysis A:Chemical,1999,139(01):11. |
[17] | Dolphin D;Traylor T G;Xie L Y .[J].Accounts of Chemical Research,1997,30(06):251. |
[18] | Lyons J E;Ellis P E Jr .[J].Catalysis Letters,1991,8(01):45. |
[19] | Ellis P E Jr;Lyons J E .[J].Coordination Chemistry Review,1990,105(01):181. |
[20] | Moore KT.;Therien MJ.;Horvath IT. .Mechanistic studies of (porphinato)iron-catalyzed isobutane oxidation. Comparative studies of three classes of electron-deficient porphyrin catalysts[J].Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics,2000(15):3125-3139. |
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