Lactone Ring-Opening Equilibria in Methanol by 1H NMR Analysis: An Assessment of the Ring-Opening Polymerizability of Lactone Monomers

The purpose of this study was to learn if a convenient 1H NMR method could be developed to serve as a tool for estimating the propensity of a given lactone to participate in ring-opening transesterification polymerization (ROTEP). The methanolysis of each of 18 lactones was initially examined in CD3OD solution in the presence of sulfuric acid as a Brønsted catalyst at ambient temperature. Once equilibrium was established, the ratio of remaining lactone to the ring-opened methyl ester/alcohol could be readily measured by NMR spectroscopy. The observed thermodynamic driving force observed for the methanol ring openings is roughly in line with the extent of ROTEP for the various classes of lactones. This is the case even though the reaction conditions for these methanolyses versus ROTEP reactions are substantially different. Qualitative evaluations of the rates of the ring-opening methanolyses were also performed, and several non-obvious relative reactivities were observed. Finally, employing this simple NMR methanolysis using low concentrations of methanol in CDCl3 is recommended as the preferred protocol for the initial evaluation of the polymerizability of any new lactone monomer that researchers may prepare in the future.