Conformational study of poly(N-propargylamides) having bulky pendant groups

被引:118
作者
Tabei, J [1 ]
Nomura, R [1 ]
Masuda, T [1 ]
机构
[1] Kyoto Univ, Grad Sch Engn, Dept Polymer Chem, Kyoto 6068501, Japan
关键词
D O I
10.1021/ma020320y
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
N-Propargylamides having chiral centers at the a-carbon of the amide groups, 1-3, were polymerized with (nbd)Rh+[eta(6)-C6H5B-(C6H5)(3)] to afford polymers with moderate molecular weights (M. = 6000-32 000) in good yield. The H-1 NMR spectra demonstrated that the polymers have stereoregular structures (cis = 100%). The polymers were proven to take a helical conformation with an excess of onehanded screw sense in CHCl3, which was supported by their intense CD effects and large optical rotations. It was confirmed that the helical structure was stabilized not only by the steric repulsion but also by the intramolecular hydrogen bonds between the pendant groups. CD spectroscopic study showed that the helical structure is more stable than that of the polymers without a branch at the a-position, which allowed the polymers to exist in the helical state in various solvents. The electronic absorption, CD effects, and optical rotations of the polymers closely correlated to the extent of the hydrogen bonding between the pendant amide groups.
引用
收藏
页码:5405 / 5409
页数:5
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