Hans Lesiecki

Das Verhalten von (Halogen)Acyldiphenylphosphinen gegenüber molekularem Sauerstoff in Abhängigkeit vom Acylrest / Behavior of (Halogeno) Acylphosphines Towards Molecular Oxygen in Dependence of the Acyl Residue

The halogenated acylphosphines RC(O)PPh2 (1a-f) [R = ClCH2 (a), FCH2 (b), F2CH (c), C2F5 (d), C3F7 (e), C6F5 (f)], which can be oxidized by rigorously dried oxygen to the phosphine oxides RC(O)P(O)Ph2 (2a-f), are obtained by reaction of NaPPh2 with the acyl chlorides RC(O)Cl. From 2a-f and stoichiometric amounts of water the alcohols RC[Ph2P(O)]2OH (3a-f) are formed. While 3c-f are isomerized into the phosphinates RC[Ph2P(O)][OP(O)Ph2]H (4c-f), the alcohols 3a, b are stable. The hydrolytic and thermal behavior of the phosphine oxides 2 and the alcohols 3 are discussed regarding the nature of the acyl residue.