Abstract
The aldol condensation-type of group transfer polymerization (aldol-GTP) of E- and Z-isomers of 1-butadienyloxytrimethylsilane (BdTMS), 3-methyl-1-butadienyloxytrimethylsilane (MeBdTMS), and 3-phenyl-1-butadienyloxytrimethylsilane (PhBdTMS) was examined in the presence of p-anisaldehyde as an initiator and ZnBr2 as a catalyst. E-Isomers were rapidly polymerized to yield their polymers with a fairly narrow molecular weight distribution (Mw/Mn=1.2—1.3), while Z-isomers could not be at all E-BdTMS was treated with excess benzaldehyde in the presence of a small amount of ZnBr2 to yield an 1:1 aldol adduct. However, Z-BdTMS reacted slower than E-BdTMS under the same conditions. The different behavior between geometrical isomers suggests that propagation of aldol-GTP proceeds by way of a bicyclic transition state, in which only the E-isomer must be fit for stereochemical requirement.
Similar content being viewed by others
Article PDF
References
T. Hirabayashi, T. Ito, and K. Yokota, Polym. J., 20, 1041 (1988).
T. Hirabayashi, T. Kawasaki, and K. Yokota, Polym. J., 22, 287 (1990).
H. Sumi, T. Hirabayashi, Y. Inai, and K. Yokota, Polym. J., 24, 669 (1992).
H. Sumi, A. Suzuki, T. Hirabayashi, Y. Inai, and K. Yokota, Polym. J., 26, 705 (1994).
Y. Mori, H. Sumi, T. Hirabayashi, Y. Inai, and K. Yokota, Macromolecules, 27, 1051 (1994).
S. Danishefsky and T. Kitahara, J. Org. Chem., 40, 538 (1975).
G. Demailly, J. B. Ousset, and C. Mioskowski, Tetrahedron Lett., 25, 4647 (1984).
C. J. Schmidle and P. G. Barnett, J. Am. Chem. Soc., 72, 3209 (1956).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Sumi, H., Haraguchi, K., Inai, Y. et al. Aldol Condensation-Type of Group Transfer Polymerization of 1-Butadienyloxytrimethylsilane and 3-Substituted-1-butadienyloxytrimethylsilanes: Different Polymerizability of Geometrical Isomers. Polym J 26, 1262–1269 (1994). https://doi.org/10.1295/polymj.26.1262
Issue Date:
DOI: https://doi.org/10.1295/polymj.26.1262