The anomalous hydrolytic behavior of 1-phenylvinyl phosphate.
The kinetics of hydrolysis of 1-phenylvinyl phosphate, 1, were studied over a pH range of 1 to 8.3 and over a pD range of 1 to 5.6 at 25 degrees C and mu = 0.5 M with sodium chloride. The hydrolytic behavior of 1 was found to differ, in many respects, from that of alkyl and aryl phosphomonoesters. First, the rates of hydrolysis of 1 were extremely rapid and, in the hydronium ion-catalyzed region, gave a solvent deuterium isotope effect (kH/kD) of 3.20. Also, the 1H-NMR spectrum of acetophenone formed upon complete hydrolysis of 1 in D2O (pD 1.2) revealed that only one deuterium atom was incorporated into the methyl group. Hence, the evidence was consistent with a rate-limiting and nonreversible proton transfer from the solvent to 1. In addition, using an H2 18O labeling study in conjunction with 31P-NMR analysis, the hydrolytic mechanism appeared to involve nucleophilic attack by water at both the alpha-carbon and the phosphorus atom with concurrent C-O and P-O bond fission. Second, in the pH region where the monoanionic species of 1 predominated, buffers had a pronounced catalytic effect on the hydrolysis rate; there appeared to be a normal solvent deuterium isotope effect; and the rate constant, k' o, showed a positive deviation from the established Brønsted relationship. The dissimilarities between 1 and alkyl and aryl phosphomonoesters supported the involvement of an alternate dephosphorylation pathway.(ABSTRACT TRUNCATED AT 250 WORDS)
Kearney
A S
AS
Department of Pharmaceutical Chemistry, University of Kansas, Lawrence 66045.
Stella
V J
VJ
D000465:Algorithms; D002851:Chromatography, High Pressure Liquid; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D009682:Magnetic Resonance Spectroscopy; D009943:Organophosphorus Compounds / Q000032:analysis / Q000737:chemistry*; D014753:Vinyl Compounds / Q000032:analysis / Q000737:chemistry*
D009943:Organophosphorus Compounds; D014753:Vinyl Compounds; C075265:1-phenylvinyl phosphate