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Spillane, WJ,Hogan, G,McGrath, P,King, J
1998
February
Journal Of The Chemical Society-Perkin Transactions 2
Aminolysis of sulfamate esters in chloroform - nonlinear kinetics
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MECHANISM ACETONITRILE SOLVENTS
309
313
Aminolysis in chloroform of sulfamate esters RNHSO2OC6H4NO2-4 principally with a series of imidazoles gives good k(obs) first-order rate constants under pseudo-first conditions. Plots of k(obs) vs. [amine] display downward curvature leading to saturation and these plots can be fitted to the rate law k(obs) = K(m)k(1)[amine]/{1 + K-m[amine]} where K-m and k(1) are defined by eqn. (i). The Hammett rho value for the[GRAPHICS]formation of the complex [S . Amine] is +1.64. Using data derived for the rate-determining step, the breakup of the intermediate is shown to be unimolecular with a rho(aryl) (substituents in the R part of S) of -1.78 consistent with an E1cB process. Steric effects of the bound-amine in the complex are negligible.
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