The hydrocarboxylation of propene with PdCl2(PPh3)2 as catalyst precursor has been studied with MeOH, EtOH, PrOH, Me2CHOH, Me2CHCH2OH, EtCHMeOH, BuOH, and Me3COH. This reaction occurs in high yields in every case, except with Me3COH, in 3-15 h, at 90-130°:, under PCO ranging from 120 to 40 atm. Qual., the reactivity order is primary > secondary > tertiary alcs. The selectivity towards the straight-chain isomer increases on (I) decreasing the temp. or (II) increasing the catalyst concn.; when BuOH is used the selectivity is insensitive to PCO in 40-120 atm., insensitive to HCl when added in 2 equivs per mol of catalyst precursor, and increases in the presence of PPh3.
Metals in organic syntheses. I. Propene hydrocarboxylation with various alkanols anddichlorobis(triphenylphosphine)palladium as catalyst precursor
TONIOLO, Luigi
1979-01-01
Abstract
The hydrocarboxylation of propene with PdCl2(PPh3)2 as catalyst precursor has been studied with MeOH, EtOH, PrOH, Me2CHOH, Me2CHCH2OH, EtCHMeOH, BuOH, and Me3COH. This reaction occurs in high yields in every case, except with Me3COH, in 3-15 h, at 90-130°:, under PCO ranging from 120 to 40 atm. Qual., the reactivity order is primary > secondary > tertiary alcs. The selectivity towards the straight-chain isomer increases on (I) decreasing the temp. or (II) increasing the catalyst concn.; when BuOH is used the selectivity is insensitive to PCO in 40-120 atm., insensitive to HCl when added in 2 equivs per mol of catalyst precursor, and increases in the presence of PPh3.
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