Hydroesterification hydroalkoxycarbonylation and Related Reactions

An inverse aqueous/organic biphasic approach for separation of catalyst and product is available with amphiphilic phosphines bearing amino groups. N-Bis (N, N -diethyl-2-aminoethyl)-4-aminomethylphenyl diphenylphosphine (N3P) was used in aqueous acidic media to modify and solubilize the palladium catalyst formed in situ from [PdCl2(PhCN)2] for hydrocarboxylation of 2-pentenoic acid to adipic acid [32]. Reaction carried out at 100 °C, pco = 50bar showed best 

Alcohol Solvent [bmimJX Ligand added Conversion (%) Rbr(%)  

The first hydrocarboxylation of 1-octene with [PdCl2(PhCN)2] performed in microemulsions of water with SCCO2 showed improved selectivity to the desired adds compared to aqueous/organic biphasic catalysis [33]. This was possible with tris (p-trifluoromethylphenyl) phosphine as well as when fluorinated surfactant was applied. At 90°C and pco = 30bar turnover frequendes 5h were observed. Chemoselectivity to the desired nonanoic add reached 90% with the n/iso ratio varying from 60 40 to 89 11. Isolation of products required extraction with diethyl ether. 

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