Optically active poly[thio-1-(N,N-diethylaminomethyl) ethylene]

Poly[thio-1-(N,N-diethylaminomethyl) ethylene] [poly(TDAE)] of different optical purities were prepared by stereoelective polymerization of racemic N,N-diethyl-N-(thiirane-2-ylmethyl) amine (TDAE) using a (1:1) $\text{ZnEt}{}_2\text{R}$ (?) 3,3-dimethyl 1,2-butanediol (R(?)DMBD) chiral initiator system. Optically enriched TDAE samples were isolated as residual monomers. These monomers were thermally polymerized to give optically active poly(TDAE) with randomly distributed R and S repeat units in various proportions. The configuration of the enantiomer preferentially incorporated into growing chains during the stereoelective polymerization was determined as R on the basis of the presence of a positive Cotton effect at 260 nm in the c.d. spectrum of residual monomers. This configuration agrees well with the known homosteric character of the $\text{ZnEt}{}_2\text{(?)}\text{DMBD}$ initiator system. ¹³C n.m.r. spectra of the different optically active poly(TDAE) samples and those of more or less stereoregular racemic ones were compared. It was found that the carbon atom of the main chain methine group is the only one which is stereosensitive. Observed triad effects were used to determine the degree of isotacticity of optically active poly(TDAE)s prepared by thermal polymerization of partly enriched monomers. The stereoelectivity of the initiator system and the optical activity of optically pure TDAE and poly(TDAE) were deduced. Side-chain nitrogen atoms did not show any competitive effect with sulphur atoms in the coordination process to the chiral initiator system.