METALS IN ORGANIC SYNTHESES .1. PROPENE HYDROCARBOXYLATION WITH VARIOUS ALKANOLS AND PDCL2(PPH3)2 AS CATALYST PRECURSOR

The hydrocarboxylation of propene with PdCl2(PPh3)2 as catalyst precursor has been studied with MeOH, EtOH, n- and iso-PrOH, and n-, iso-, s-, and t-BuOH. this reaction occurs in high yields in every case, except with t-BuOH, in 3 - 15 h, at 90 - 130 °C, under PCO ranging from ca 120 at ca. 40 atm. Qualitative observations indicate the following apparent reactivity order: primary > secondary > tertiary alcohols. The selectivity towards the straight-chain isomer increases on (i), decreasing the temperature or (ii) increasing the catalyst concentration; when n-BuOh is used the selectivity is insensitive to PCO in the range studied (40 - 120), insensitive to HCl when added in 2 equivalents per mole of catalyst precursor, and increases in the presence of PPh3. © 1979.