POLYISONITRILES .3. SYNTHESIS AND RACEMIZATION OF OPTICALLY ACTIVE POLY(ALPHA-PHENYLETHYLISONITRILE)

The homopolymerizations of d- and of ɭ-α-phenylethylisonitrile have been successfully achieved with retention of configuration employing the catalyst system of Millich and Sinclair. The respective polymers of high molecular weight show specific rotations of the same sign yet tenfold greater magnitude than the monomers (i.e., polymer samples, [α]27D ~400°, M27D =500 deg cm2/g). The results tend to support one of two tentative assignments for the structure of the mer, although cautious interpretation shows the results not to be conclusive. Thermal racemization of the optically active polymer in refluxing toluene gives evidence of more than one process taking place, and reveals the generation of chromophores which absorb in the range of 310–390 nm. Nmr spectra of d-poly(α-phenylethylisonitrile), at 27 and 128°, are given. © 1969, American Chemical Society. All rights reserved.