Arylphosphonic acids. II. General acid and general base catalysis of acetone enolization

We have measured the rate constants for the enolization of acetone catalyzed by 29 arylphosphonate dianions (ArPO32−) and by 20 arylphosphonic acids (ArPO3H2). An excellent Brønsted correlation is found for the former reaction, with most ortho substituted compounds falling on the line drawn for the meta and para compounds (β = 0.72). The largest deviation is found for o-iodo, whose small positive deviation is ascribed to a polarizability effect in the transition state. The arylphosphonic acids give a fairly good Brønsted plot (α = 0.37) but here the ortho substituents tend to react slightly faster than would be expected on the basis of their equilibrium acid strengths. Catalysis by the monoanion ArPO3H− is difficult to detect; such ions appear to be acting as general acids, not general bases, and do not appear to act as bifunctional catalysts; it is shown that protonating acetone is 3.4 × 104 times as effective as deprotonating ArPO3H−. The Brønsted coefficients (β) for the rate-controlling steps for the enolization of acetone by the principal routes are shown to be inversely related to the magnitude of the rate constants.