Many compounds containing a sulfamate moiety, such as NH2SO2O- are now known to be medicinally important. However, very little is known about their mechanisms of reaction even under non-biological conditions. In this work the various types of elimination mechanisms that may occur have been probed by studying the kinetics of the reactions of model sulfamate substrates with amines (bases) that act as models for the enzymes involved. The principal mechanistic tool employed has been Bronsted plots and both 'normal' rectilinear and two types of biphasic plots have been found for the decomposition of the esters in acetonitrile (ACN). The mechanisms operating are seen as being of the E2 and E1cB types. Copyright (c) 2006 John Wiley & Sons, Ltd.