The kinetics of hydrolysis at medium acid strength (pH interval 2–5) of a series of phenylsulfamateesters1 have been studied and they have been found to react by an associative SN2(S) mechanism with water acting as a nucleophile attacking at sulfur, cleaving the S–O bond with simultaneous formation of a new S–O bond to the oxygen of a water molecule leading to sulfamic acid and phenol as products. In neutral to moderate alkaline solution (pH ≥ 6–9) a dissociative (E1cB) route is followed that involves i) ionization of the amino group followed by ii) unimolecular expulsion of the leaving group from the ionized ester to give N-sulfonylamine [HNSO2] as an intermediate. In more alkaline solution further ionization of the conjugate base of the ester occurs to give a dianionic species which expels the aryloxide leaving group to yield the novel N-sulfonylamine anion [−NSO2]; in a final step, rapid attack of hydroxide ion or a water molecule on it leads again to sulfamic acid. A series of substituted benzyl 4-nitrophenylsulfamateesters4 were hydrolysed in the pH range 6.4–14, giving rise to a Hammett relationship whose reaction constant is shown to be consistent with the E1cB mechanism.
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Organic & Biomolecular Chemistry
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