MECHANISM AND MICELLAR CATALYSIS OF ACID CLEAVAGE OF ALPHA-PHENYLVINYL DIETHYL PHOSPHATE

The acid cleavage of α-phenylvinyl diethyl phosphate follows an A-Se2 mechanism. Plots of log kψ against -Ho‘ are linear with slopes 1.07-1.4 for hydrochloric, perchloric, and sulfuric acids, with -φ = 0.2-0.6. In moderately concentrated acid the Arrhenius parameters depend on both acidity and temperature, but in dilute acid δS* = -8.8 eu, [formula-omitted] = 2.5, and the positive salt effect of LiClO4 is greater than that of LiCl, although LiClO4 “salts in” and LiCl “salts out” the substrate. At concentrations above the cmc, sodium lauryl sulfate is an effective catalyst of the acid cleavage and [formula-omitted] 2.2. The catalysis is inhibited by cations with the rate sequence no salt > Li + > Na + >> (CH3)3N+. © 1969, American Chemical Society. All rights reserved.