Abstract
The mutarotation between form I and form II of poly(cis‐5‐ethyl‐D‐proline) has been experimentally realized. A number of hydrogen‐bond‐forming solvents have been found effective in initiating the mutarotational process. The rate of mutarotation seems to be proportional to the acidity of the active solvent. The enthalpy of activation energy for the mutarotation is estimated from the first‐order kinetics at the lower conversion by means of the Arrhenius equation to be approximately 16.7 kcal/mol. The solvent‐polymer interactions are proven to be one of the important driving forces for the mutarotation. The specific site at which hydrogen bonding takes place has been determined to be the carbonyl group of the amide by infrared spectroscopic techniques. The molecular reason for the greater susceptibility of poly(cis‐5‐ethyl‐L‐proline) II to the solvent effect than poly(cis‐5‐ethyl‐L‐proline) I can be satisfactorily explained by the relatively more extended structure of form I than form II. The mechanism for the mutarotation undoubtedly involves a cis‐trans isomerization of the amide bond. The conformation of the transient states during the mutarotational process is still evidently helical in nature, probably consisting of long poly(cis‐5‐ethylproline) I and II segments.