Peer-Reviewed Journal Details
Mandatory Fields
Spillane, WJ,McGrath, P,Brack, C,Barry, K
1998
May
Chemical Communications
Novel change in rate-determining step within an E1cB mechanism during aminolysis of a sulfamate ester in acetonitrile
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ELIMINATION-REACTIONS HYDROLYSIS INTERMEDIATE
1017
1018
The observation of biphasic Bronsted plots (beta(1) Ca. 0.7 and beta 2 Ca. 0) in the aminolysis (alicyclic amines, pyridines) of 4-nitrophenyl N-benzylsulfamate 1a in MeCN is interpreted as being due to a mechanistic change from (ElcB)(irrev) to (ElcB)(rev); the change in rate-determining step occurs at approximately the pK(a) of 1a and other more basic substrates give straight line plots; an entropy study supports the change from a bimolecular to a unimolecular mechanism.
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