氟两相体系中的有机缩合反应
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摘要
用相应的稀土氯化物或氧化物和全氟辛基磺酸反应来制备了RE(OPf)_3(RE=Yb，Sc，Y，La，Eu，Tm)。并以DSC、ICP、IR和元素分析等手段对其进行了表征。
以Yb(OPf)_3为催化剂，选取全氟萘烷(C_(10)F_(18))为全氟溶剂，对Knoeveagel缩合反应、Diacetates缩合反应及Baylis-Hillmann缩合反应进行了研究。研究表明Yb(OPf)_3和全氟萘烷(C_(10)F_(18))组成的氟两相体系能有效的催化上述缩合反应。考察了温度、时间、催化剂用量和氟相与有机相相比等条件对Knoeveagel缩合反应和Diacetates缩合反应的影响。对反应机理进行了推测。含有催化剂的氟相通过简单的相分离，就可回收利用，氟相重复使用5次，其催化活性无明显降低。
The catalysts of rare earth(Ⅲ) perfluorooctanesulfonates (RE(OPf)_3, RE=Yb, Sc, La,Eu, Tm, Y) were prepared from either rare earth chlorides(Ⅲ) or oxides andperfluorooctane sulfonic acid. The perflates obtained were characterized by DSC, ICP, IR,and elemental analysis.
Yb(OPf)_3 acted as a efficient catalyst for Knoevenagel condensation, Diacetatescondensation, Baylis-Hillmann condensation, in fluorous biphasic system usingperfluorodecalin (C_(10)F_(18), cis and trans-mixture) as fluorous solvent. Effects of reactiontemperature, reaction time, amount of catalyst, and the ratio of fluorous phase/organicphase on Knoevenagel and Diacetates reactions were investigated. The reactionmechanisms were proposed. By simple phase separation the fluorous phase containingcatalyst could be re-utilized up to five times only with a little decrease in activity.
以Yb(OPf)_3为催化剂，选取全氟萘烷(C_(10)F_(18))为全氟溶剂，对Knoeveagel缩合反应、Diacetates缩合反应及Baylis-Hillmann缩合反应进行了研究。研究表明Yb(OPf)_3和全氟萘烷(C_(10)F_(18))组成的氟两相体系能有效的催化上述缩合反应。考察了温度、时间、催化剂用量和氟相与有机相相比等条件对Knoeveagel缩合反应和Diacetates缩合反应的影响。对反应机理进行了推测。含有催化剂的氟相通过简单的相分离，就可回收利用，氟相重复使用5次，其催化活性无明显降低。
The catalysts of rare earth(Ⅲ) perfluorooctanesulfonates (RE(OPf)_3, RE=Yb, Sc, La,Eu, Tm, Y) were prepared from either rare earth chlorides(Ⅲ) or oxides andperfluorooctane sulfonic acid. The perflates obtained were characterized by DSC, ICP, IR,and elemental analysis.
Yb(OPf)_3 acted as a efficient catalyst for Knoevenagel condensation, Diacetatescondensation, Baylis-Hillmann condensation, in fluorous biphasic system usingperfluorodecalin (C_(10)F_(18), cis and trans-mixture) as fluorous solvent. Effects of reactiontemperature, reaction time, amount of catalyst, and the ratio of fluorous phase/organicphase on Knoevenagel and Diacetates reactions were investigated. The reactionmechanisms were proposed. By simple phase separation the fluorous phase containingcatalyst could be re-utilized up to five times only with a little decrease in activity.
引文
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[16] 易文斌．氟两相体系中的有机缩合反应[M]．南京理工大学博士论文．2006，3
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[1] 钱长涛，杜灿屏．稀土金属有机化学．第一版．北京：化学工业出版社，2004
[2] Wilkinson G, Birmingham J M. Cyclopentadienyl compounds of Sc, Y, La, Ce and some lanthanide elements[J]. J Am Chem Soc. 1954, 76(23): 6210-6218
[3] Kagan H B. Frontiers in Lanthanide Chemistry[J]. Chem Rev. 2002, 102(6): 1805-2476
[4] Lappert M F, Wvans W J, Mingos D M P. Advanced in the Organometallics Chemistry of the Group 3 and Lanthanoid Elements[J]. J Organometallic Chem. 2002:647-650
[5] Imamoto T. Lantnanides in Organic Synthesis. 1st, London: Academic Press, 1994
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