Kinetics and mechanism of the reaction of dimethyl acetylphosphonate with water. Expulsion of a phosphonate ester from a carbonyl hydrate

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Abstract
Dimethyl acetylphosphonate (DAP) is rapidly cleaved in water to acetate and dimethylphosphonic acid. The half time for reaction at pH 7, 25 °C is estimated to be 3 s. The reaction is first order in hydroxide ion concentration and first order in DAP concentration. Rates of reaction were measured over the pH range 3.8 to 6.5 at 25 °C, 6.5 and 7.0 at 5 °C, 4.5 to 6.5 at 35 °C, and 4.5 to 6.0 at 45 °C. The average observed second-order rate constant at 25 °C is 2.4 × 106M−1 s−1. DAP is converted rapidly to a hydrated carbonyl adduct. The mechanism for the formation of the observed products is proposed to be analogous to cleavage reactions of other carbonyl hydrates, proceeding from a monoanion conjugate in this case. The estimated rate constant for the unimolecular cleavage of the carbonyl hydrate anion is 2 × 103 s−1. The rapid hydrolysis of DAP results from energetically favourable formation of a hydrate due to the electronic effect of the phosphonate diester. This effect also promoles ionization of the hydrate. The ionized hydrate readily expels the phosphonate diester to achieve the overall rapid hydrolysis.

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