Abstract
Polymerization of the two stereoisomers (1a and 1e) of 4-bromo-6,8-dioxabicyclo[3.2.1]octane was carried out in methylene chloride at different temperatures ranging from −90 to 0°C. Antimony pentafluoride, antimony pentachloride, and trifluoromethanesulfonic acid were found effective for the homopolymerization of the equatorially substituted isomer (1e). Isomerization of 1e to the axially substituted counterpart (1a) occurred during the polymerization at −30°C or above to provide a copolymer of 1e and 1a, especially when trifluoromethanesulfonic acid was used as an initiator. 13C-NMR analysis of the resulting polymers disclosed that the polymer of 1e prepared at −90°C entirely consisted of a structural unit (α-form) in which the exocyclic acetal oxygen atom was axially oriented to the tetrahydropyran ring in a repeating unit. With the rise in polymerization temperaure, the fraction of the other structural unit (β-form) in which the exocyclic acetal oxygen lies in the equatorial position of the tetrahydropyran ring increased appreciably. Polymerization of stereoisomer mixtures of 1a and 1e was induced even with boron trifluoride etherate which is an ineffective initiator for the homopolymerization of 1e. Irrespective of the reaction conditions, the relative reactivity of 1a was higher than that of 1e. The difference in the reactivity between the stereoisomers are discussed in comparison with those of 6,8-dioxabicyclo[3.2.1]octane and anhydrosugar derivatives having the identical skeleton.
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Okada, M., Sumitomo, H. & Sumi, A. Polymerization of Bicyclic Acetals. IX. Cationic Polymerization of 4-Bromo-6,8-dioxabicyclo[3.2.1]octane. Polym J 14, 59–68 (1982). https://doi.org/10.1295/polymj.14.59
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DOI: https://doi.org/10.1295/polymj.14.59
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