Acid-promoted double ring-opening reaction of bicyclobis (γ-butyrolactone) with alcohol and its application to polyester synthesis

Abstract

Bicyclobis(γ-butyrolactone) (BBL) bearing methyl group 1a reacted with benzyl alcohol (BnOH) in the presence of p-toluenesulfonic acid (p-TsOH) through the double ring-opening of the bislactone structure to afford the corresponding adduct 2a bearing carboxyl group. The resulting carboxyl group underwent condensation with BnOH to afford the corresponding diester 3a. The second step was quite slow at ambient temperature; however, it was efficiently accelerated by elevating temperature to 120 °C or performing under reduced pressure at 80 °C to afford 3a in an excellent yield. Based on these results, the reaction of 1a with xylene-α,α-diol (XyD) was carried out in chlorobenzene at 120 °C to obtain the corresponding polyester bearing ketone group in the side chain. The condensation reaction in the second step was effectively promoted by simultaneous removal of water under reduced pressure. BBLs 1b and 1c bearing reactive groups, isopropenyl and chloromethyl, respectively, were also employed as monomers efficiently. Their reactions with XyD gave the corresponding reactive polyesters bearing methacryloyl and chloroacetyl moieties, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011