FACILE CATALYST SEPARATION WITHOUT WATER - FLUOROUS BIPHASE HYDROFORMYLATION OF OLEFINS
FACILE CATALYST SEPARATION WITHOUT WATER - FLUOROUS BIPHASE HYDROFORMYLATION OF OLEFINS
复制标题
DOI：
10.1126/science.266.5182.72
复制
发表时间：
1994-10-07
期刊：
影响因子：
56.9
通讯作者：
RABAI, J
中科院分区：
文献类型：
--
作者：
HORVATH, IT;RABAI, J
基于部分或全氟化合物与非氟化合物的有限混溶性，已经发展出一种进行化学计量和催化化学转化的新概念。含氟双相体系（FBS）由含溶解试剂或催化剂的氟相和另一相组成，该相可以是在氟相中溶解度有限或无溶解度的任何常见有机或无机溶剂。含氟相被定义为两相体系中富含氟碳（主要是全氟烷烃、醚和叔胺）的相。FBS相容试剂或催化剂含有足够多的氟基团，使其只溶于或优先溶于氟相。最有效的氟基团是高碳数的线性或支链全氟烷基链；它们也可能含有杂原子。化学转变既可以发生在含氟相，也可以发生在两相界面。在甲苯中萃取铑和烯烃的氢甲酰化反应中证明了FBS的应用。在温和条件下将催化剂或试剂从产品中完全分离的能力可能导致均相催化剂或试剂的工业应用，并开发更环保的工艺。
A novel concept for performing stoichiometric and catalytic chemical transformations has been developed that is based on the limited miscibility of partially or fully fluorinated compounds with nonfluorinated compounds. A fluorous biphase system (FBS) consists of a fluorous phase containing a dissolved reagent or catalyst and another phase, which could be any common organic or nonorganic solvent with limited or no solubility in the fluorous phase. The fluorous phase is defined as the fluorocarbon (mostly perfluorinated alkanes, ethers, and tertiary amines)-rich phase of a biphase system. An FBS compatible reagent or catalyst contains enough fluorous moieties that it will be soluble only or preferentially in the fluorous phase. The most effective fluorous moieties are linear or branched perfluoroalkyl chains with high carbon number; they may also contain heteroatoms. The chemical transformation may occur either in the fluorous phase or at the interface of the two phases. The application of FBS has been demonstrated for the extraction of rhodium from toluene and for the hydroformylation of olefins. The ability to separate a catalyst or a reagent from the products completely at mild conditions could lead to industrial application of homogeneous catalysts or reagents and to the development of more environmentally benign processes.