Abstract
The t-butoxy-initiated, acetate end-capped, purely-isotactic oligomers of trichloroacetaldehyde (chloral)—from dimer to nonamer—were resolved into the two enantiomers (RRR···R and SSS···S isomers) by HPLC using a chiral stationary phase. The (−)-isomer eluted faster than the (+)-isomer for each oligomer racemate. The (−)-isomers were identified as the RRR···R isomers which exist in a right-handed 41-helical conformation in solution as well as in the crystalline state. The specific rotation of the oligomer in solution was not significantly dependent on the degree of polymerization, and gave a value, [α]D=−23.7° in chloroform for the (−)-pentamer. CD spectra of the optically pure dimer and pentamer were also examined.
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Ute, K., Oka, Ki., Okamoto, Y. et al. Haloaldehyde Polymers LIII. Optical Resolution of Purely Isotactic Oligomers of Chloral: Optical Activity of the Chloral Oligomers Assuming One-Handed Helical Conformation in Solution. Polym J 23, 1419–1424 (1991). https://doi.org/10.1295/polymj.23.1419
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DOI: https://doi.org/10.1295/polymj.23.1419