Hydrolysis of the Vinyl Ether Functional Group in a Model for Prostacyclin in Which the Carboxyl Group Has Been Replaced by a Pyridine Ring

Article abstract of DOI:10.1021/jo00270a023

The hydrolysis of the vinyl ether functional group in the three isomeric compounds (Z,E)-2-methoxy-6-(2-pyridyl)hex-2-ene (3 and 4) and 2-methoxy-6-(2-pyridyl)hex-1-ene (5) has been studied in hydrochloric acid solutions and acetic acid and biphosphate ion buffer solutions.The rate constant ratio for the hydronium ion catalysis of the neutral and positive forms of the substrates are 45.7, 44.9 and 15.7, respectively.The rate accelerations are interpreted in terms of intramolecular general acid catalysis and the results are discussed in relation to the suggested mechanism for hydrolysis of prostacyclin.