Hydroformylation of Functionalised Olefins

5 Hydroformylation of Functionalised Olefins - Introduction of polar substituents such as -C02Me into the alkyl chain of a-olefins considerably extends the scope of Rh/tppts-catalysed hydroformylation in aqueous/organic two phase systems.89,417 

The polarity of the lower and mid range terminally unsaturated esters up to 

11- formylundecanoate and branched 10-formylundecanoate were 92/8 in the absence of tensides, 86/14 with anionic, 80/20 with zwitterionic and 70/30 with cationic surfactants.89,417 The catalyst was recovered by phase separation and 

DSM jointly with Du Pont de Nemours308 have patented platinum catalysts generated from the water soluble sulfonated ligand 30 (Table 2 m=0, n=0, m=l, n=2 m=l, n=l, Ar=nBu-S03Li) and used in the aqueous phase hydroformylation of internally unsaturated carboxylic acids, esters or nitriles to their corresponding formyl derivatives which are useful intermediates for the preparation of di-carboxylic acids (e.g. adipic acid). For example, TOFs up to 105 h-1 were achieved in the hydroformylation of 3-pentenoic acid catalysed by Pt/30 (m=0, n=0) at 100°C and 80 bar CO/H2 to give aldehydes with a selectivity of 83% (n/i=3.4), valeric acid (4.6%) and adipic acid (8.1%).308 The products were separated from the aqueous catalyst solution by extraction with ether. Five recycles of the aqueous catalyst solution showed that the Pt/30 (m=0, n=0) catalyst retains its activity. 

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