Catalytic deuterium exchange reactions with organics. LXXI. Homogeneous platinum catalysed deuteration of the long-chain alkylbenzenes. Relationship toalkane exchange

Abstract

The long-chain alkylbenzenes out to nonylbenzene have been exchanged with D2O in the presence of homogeneous platinum, deuteration occurring in both ring and side chain. ortho-Deactivation in the ring is observed, consistent with a mechanism involving a π-dissociative process. Total isotope incorporation in a particular compound decreases with increase in length and degree of branching of the side chain. In the side chain α and terminal positions deuterata predominantly, degree of isotope incorporation in these positions decreasing gradually down the series to nonylbenzene. For butylbenzene and higher homologues, deuteration of methylene positions is low. Orientation of isotope in the side chain of l',l?-dimethylpropylbenzene is unique and is used as a basis for a novel terminal abstraction π-complex (TAPC) mechanism proposed to explain terminal exchange in the alkylbenzenes. Concepts involving 'inner' and 'outer' π-complexes are shown to be of value in discussing mechanisms of exchange in other positions of these compounds. The data may be related to mechanisms for simple alkane exchange using this same catalyst.