Biphasic catalysis hydroformylation

The term Supported Ionic Liquid Phase (SILP) catalysis has recently been introduced into the literature to describe the heterogenisation of a homogeneous catalyst system by confining an ionic liquid solution of catalytically active complexes on a solid support [68], In comparison to the conventional liquid-liquid biphasic catalysis in organic-ionic liquid mixtures, the concept of SILP-catalysis offers very efficient use of the ionic liquid. Figure 7.10 exemplifies the concept for the Rh-catalysed hydroformylation. 

Nevertheless, the application of ionic liquids in the liquid-liquid, biphasic Rh-catalysed hydroformylation offers technically interesting advantages vs. the traditional aqueous biphasic catalysis e.g. much higher solubility for longer chain olefins and the compatibility of the ionic liquid with phosphite ligands [51]. 

For instance, catalysis in liquid/liquid two phases is generally referred to as biphasic catalysis and has widened the practical scope of homogeneous catalysis the catalyst is present in one liquid phase, while reactants and products are present in the other liquid phase. Thus, the catalyst can be separated by simple phase separation. Celanese is operating a 300 000 t/a plant for propylene hydroformylation using a water-soluble rhodium phosphine complex in a biphasic mode of operation at the Ruhrchemie site in Oberhausen [142],... 

The consequence of low alkene solubihty is in that industrially the RCH-RP process can be used only for the hydroformylation of C2-C4 olefins. In all other cases the overah production rate becomes unacceptably low. This is what makes the hydroformylation of higher olefins one of the central problems in aqueous/organic biphasic catalysis. Many solutions to this problem have been suggested (some of them will be discussed below), however, any procedure which increases the mutual solubihty of the organic components and the aqueous ingredients (co-solvents, surfactants) may... 

The use of surfactants in hydrogenation and hydroformylation immediately followed the practical implementation of the original idea of aqueous biphasic catalysis [57, 118]. Not only the effect of well-known tenzides (SDS, CTAB, etc.) was studied, but new amphiphilic phosphine... 

A few years ago, a new class of ligands namely the sulfonated phosphites (for examples see Table 7, 132, 133) was described.283 287 They show remarkable stabilities in water compared to conventional phosphites such as P(OPh)3 and rhodium catalysts modified with 132 exhibited much higher catalytic activities in the hydroformylation of 1-tetradecene than conventional Rh/P(OPh)3 or Ph/PPh3 catalysts even at lower reaction temperatures.285,286 Sulfonated phosphite ligands may play a role in the emerging field of biphasic catalysis in ionic liquids15 22 or in combination with membrane separation of the metal complexes of these bulky ligands. 

A chapter written in 1996 covers hydroformylation catalyzed by organometallic complexes in detail,219 whereas a review written 5 years later gives a summary of the advances on hydroformylation with respect to synthetic applications.220 A selection of papers in a special journal issue has been devoted to carbonylation reactions.221 A major area of the research has been the development of fluorous biphasic catalysis and the design of new catalysts for aqueous/organic biphasic catalysis to achieve high activity and regioselectivity of linear or branched aldehyde formation. 

The crucial problem associated with the use of homogeneous rhodium catalysts in industrial hydroformylation is catalyst recovery. Because of the high cost of rhodium, it is necessary to recover rhodium at the ppm level to ensure economical operation. A highly successful solution to this problem was the development and application of the aqueous biphasic catalysis concept. 

Because of their low solubilities in the aqueous phase, the hydroformylation of higher alkenes (>C2) is still a challenging problem. In addition to fluorous biphasic catalysis, possible solutions, which have been addressed, include the addition of surfactants240,241 or the use of amphiphilic ligands242-244 to enhance mutual solubility or mobility of the components across the phase boundary and thereby increase the rate of reaction. The use of polar solvents such as alcohols,245 p-cyclodextrin,246 cyclodextrin ligands,247 248 thermoregulated phase-transfer... 

The fluorous biphasic catalysis concept was successfully demonstrated first by hydroformylation of 1-decene carried out in perfluoromethylcyclohexane and toluene, which forms a homogeneous liquid phase at 100°C in the presence of catalyst 2 prepared in situ according to Eq. (14.1) 125,133... 

Figure 4.24 a A general process schematic for aqueous biphasic catalysis, and examples ofwater-soluble phosphine ligands b the catalytic cycle for the Ruhrchemie/Rhone-Poulenc hydroformylation of propene. 

Sellin MF, Webb PB, Cole-Hamilton DJ (2001) Continuous flow homogeneous catalysis hydroformylation of alkenes in supercritical fluid-ionic liquid biphasic mixtures. Chem Commun 8 781-782... 

Fig. 1. Fluorous biphasic catalysis part I hydroformylation, hydro-boration, and transesterification with fluorous tagged catalysts.

In the Kuraray process for the production of nonane-1,9-diol two steps involve the use of aqueous biphasic catalysis Pd/tppms catalyzed telomerization of butadiene with water as a reactant and Rh/tppms catalyzed hydroformylation (Fig. 7.14) [51]. 

As described in the introductory chapter, biphasic catalysis has been around for a long time, but despite a few notable successes such as the Shell Higher Olefin Process (SHOP) and the Rhone-Poulenc-Ruhrchemie hydroformylation process, very few biphasic processes have made it into the industrial arena. The limitations of the solvents used so far in biphasic (or multiphasic) catalysis appear to be overcome by ionic liquids, and even if the perfect ionic liquid is not yet available, then there seems to be almost no limit to the number of new ionic liquids that can be made. It has been estimated that up to 1018 different ionic liquids may exist[1 2] and with such a vast number to choose from it is essential that understanding increases in order to allow accurate predictions of their properties and functions, opening up the possibility of designer solvents. 

Fluorous biphasic catalysis was first reported with the hydroformylation reaction depicted in Figure 12.16 (Curran and Lee, 2001). 

The use of ionic liquids with SCCO2 has recently been reviewed.More information on ionic liquids can be found in Chapter 6. However, their use in biphasic catalysis with SCCO2 is discussed here. They have been used most extensively for hydrogenation and hydroformylation reactions. 

---