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.
Metals in Organic Syntheses I. Propene hydrocarboxylation with various alkanols and [PdCl2(PPh3)2] as catalyst precursor.
CAVINATO, GIANNI;
1979
Abstract
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.Pubblicazioni consigliate
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
