Synthesis and polymerization of 5‐(N,N‐dimethylamino)naphthylacetylene with homogeneous rhodium and palladium complexes

Abstract

The monomer 5‐ethynyl‐N,N‐dimethylnaphthalen‐1‐amine (2) was satisfactorily obtained by a heterocoupling reaction between 5‐iodo‐(N,N‐dimethyl)naphthalen‐1‐amine and 2‐methyl‐3‐butyn‐2‐ol catalyzed by a palladium–copper system and followed by acetone elimination. Poly(5‐ethynyl‐N,N‐dimethylnaphthalen‐1‐amine) was isolated by the reaction of 2 in the presence of homogeneous rhodium and palladium complexes. On the basis of the spectroscopic data, the polymer always showed a cis–transoidal, stereoregular structure. Moreover, only with the rhodium catalyst in methanol was a dimeric product isolated in a very low yield, having a conjugated terminal ene–yne structure, which permitted the consideration of a metallated chain‐transfer intermediate in the polymer propagation. The kinetics of the catalyzed reaction were analyzed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 437–446, 2007