Hydroformylation, using supported

Rhodium Catalysed Hydroformylation Using Supported Ionic Liquid Phase SILP) Catalysis... 

Relatively few hydroformylations using supported cobalt complexes have been reported. Moffat (78, 79) showed that poly-2-vinylpyridine reversibly reacted with both Co2(CO) and HCo(CO)4, the cobalt carbonyl being displaced by excess carbon monoxide. This enabled the polymer to pick up the cobalt carbonyl at the end of the reaction and, thus, allowed it to be separated from the products by filtration. The polymer acted as a catalyst reservoir by rapidly releasing the cobalt carbonyl into solution in the presence of further carbon monoxide, so that the actual catalysis was a homogeneous process. More recently, cobalt carbonyl has been irreversibly bound to a polystyrene resin... 

Riisager, A., Wasserscheid, P, Van Hal, R., and Fehrmaim, R. (2003) Continuous fixed-bed gas-phase hydroformylation using supported ionic liquid-phase (SILP) Rh catalysts. /. Catal., 219 (2), 452-455. 

Reiche A, Stemich T., Sandner B., Lobitz P. Fleischer G. (1995). Ion transport in gel electrolytes, Electrochimica Acta, International symposium on polymer electrolytes, vol.40, n°13-14, p>p. 2153-2157, (October 1995), ISSN 0013-4686 Riisager A, Wasserscheid P., Van Hal R. Fehrmann R. (2003). Continuous fixed-bed gas-phase hydroformylation using supported ionic liquid phase (SILP) Rh catalysts. /. Catal, vol.219, n°2, pp.452-455, (October 2003), ISSN 00219517 Robert D., Schneider M., Bom M., Mieloszynski J.L. Paquer D. (19%). Influence of heteroatomic systems on anti-wear and extreme pressure properties of organo-sulfur compounds. C, R. Acad, Set, serie Tib, vol.323, p>p.l27-132, (19%), ISSN 0320-8437 Rogers R.D. Seddon K.R. (2003). Ionic Liquids—Solvents of the Future , Scimee, Vol. 302, n°5646, pp. 792-793 (October 2003), ISSN 0036-8075 Seddon K.R. (1997). Ionic Liquids for Clean Technology, J. Chem. Technol. Biotechnol, vol. 68, n°4, pp.351-356, (April 1997), ISSN 0268-2575... 

Industrial problems have, in some instances, been solved either by a proper choice of construction materials and suitable process design or by development of heterogeneous catalytic systems using supported complexes or by generating active complexes in situ on a support material which avoid some of the problems of liquid-phase operation. For example, a number of the problems in liquid-phase vinyl acetate processing have been overcome by development of supported Pd catalysts (106). Vapor-phase hydroformylation has been carried out on supported rhodium complexes (107). 

Supported aqueous phase catalysts were developed for hydroformylation by Davis and co-workers [67]. Very hydrophobic alkenes,such as 1-octene, 1-tetra-decene, or 1-heptadecene and also oleic alcohol, were hydroformylated using... 

Related Rh systems have also been used for the hydroformylation of allyl alcohol. The competing isomerization to propionaldehyde was dependent on the presence of aluminium in silica supports and also on the Rh concentration. This could be suppressed by using supports with a very low A1 content and phosphine-rich Rh complexes. Operating at 88-108 °C and 0.1-0.4 MPa, propionaldehyde and 4-hydroxybutyraldehyde were the only products observed. This SLPC system was more active for the hydroformylation of allyl alcohol than for propene by a factor of 10-30. Similar trends have been observed earlier for homogeneous systems. ... 

Table 5.6-3 Evaluation of the hydroformylation reaction ofi-hexene to form n,iso-heptanal using supported ionic liquid phase catalysis (SILP), biphasic catalysis and homogeneous catalysis [88]...

Table 5.6-4 Continuous, gas-phase Rh-phosphine catalyzed propene hydroformylation using silica gel-based supported ionic liquid phase catalysts containing [BMIM][PF6]1 I [91] and [92]...

Tables Evaluation of the hydroformylation reaction of 1-hexene to form n,/-heptanal using supported ILcatalysis (silc), biphasic catalysis, and homogeneous catalysis [14].

Regelein, D. (2005) Hydroformylation of 1 Octene using Supported Ionic Liquid Phase (SILP) Catalysts Diploma Thesis. FAU Erlangen-Nuremherg. 

Using supported rhodium as catalyst, 2-nitrostyrene was converted into skatole in 70 % yield by CO/H2 (160 atm) in benzene at 160 °C [27]. However this reaction, conducted under hydroformylation conditions, involves formation of 2-(o-nitrophenyl)propionaldehyde by homogeneous catalysis, reduction of the nitro group by heterogeneous catalysis, and ring closure accompanied by thermal dehydration (Scheme 3) ... 

Haumann, M., Jakuttis, M., Franke, R., Schonweiz, A. and Wasserscheid, R, Continuous gas-phase hydroformylation of a highly diluted technical C4 feed using supported ionic liquid phase catalysts, ChemCatChem. 3,1822-1827 (2011). 

A particular advantage of SAP catalysis is that reaction with hydro-phobic substrates occurs at the aqueous/organic interface allowing water insoluble higher olefins to be hydroformylated using the RhH(CO)(tppts)3 system. In the biphasic hydroformylation using RhH(CO)(tppts)3 the reaction rates decrease in the order 1-hexene > 1-octene > 1-decene. In contrast, using the same catalyst in a silica supported aqueous phase similar activities and selectivities were obtained in the hydroformylation of these olefins. The low n/i ratio observed in... 

Polyquiaolines have been used as polymer supports for transition-metal cataly2ed reactions. The coordinatkig abiUty of polyqukioline ligands for specific transition metals has allowed thek use as catalysts ki hydroformylation reactions (99) and for the electrochemical oxidation of primary alcohols (100). 

Since 1985, several thousands of publications have appeared on complexes that are active as catalysts in the addition of carbon monoxide in reactions such as carbonylation of alcohols, hydroformylation, isocyanate formation, polyketone formation, etc. It will therefore be impossible within the scope of this chapter to review all these reports. In many instances we will refer to recent review articles and discuss only the results of the last few years. Second, we will focus on those reports that have made use explicitly of coordination complexes, rather than in situ prepared catalysts. Work not containing identified complexes but related to publications discussing well-defined complexes is often mentioned by their reference only. Metal salts used as precursors on inorganic supports are often less well defined and most reports on these will not be mentioned. 

TABLE 3.1. Asymmetric hydroformylation of styrene using polystyrene supported rhodium catalysts based... 

In subsequent work the same supported catalysts were used in different reactor setups [20] (Figure 3.3). A vapour-phase reactor in which the supported catalyst was mounted on a bed was used for the hydroformylation of volatile alkenes such as cis-2-butene and trifluoropropene. The initial activities and selectivity s were similar to those of the homogeneous solutions, i.e. a TOF of 114 and 90% ee in the hydroformylation of trifluoropropene was reported. No rhodium was detected in the product phase, which means less then 0.8% of the loaded rhodium had leached. The results were, however, very sensitive to the conditions applied and, especially at longer reaction times, the catalyst decomposed. In a second approach the polymer supported complex was packed in a stainless steal column and installed in a continuous flow set-up. 

The existence of two different rhodium species co-existing on the silica support can be used as an advantage by controlling their relative amount. Under standard hydroformylation conditions, the cationic species and the neutral hydride complex are both present in significant amounts. Hence hydroformylation and hydrogenation will both proceed under a CO/H2 atmosphere. Indeed a clean one-pot reaction of 1-octene to 1-nonanol was performed, using the supported catalyst for a hydroformylation-hydrogenation cascade reaction. 98 % of the 1-octene was converted in the... 

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