The Acid‐catalyzed Hydrolysis of CF3‐deactivated Diazoalkanes
Helvetica Chimica Acta1979Vol. 62(7), pp. 2218–2229
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Abstract
Abstract The acid‐catalyzed hydrolysis of CF 3 CHN 2 ( 1 ) follows an A 2 mechanism of preequilibrium protonation and rate‐determining solvolysis of the intermediate diazonium ion 4 ; this was demonstrated by: (a) the inverse kinetic isotope effect; (b) H‐D exchange; (c) the unimportance of general acid catalysis; (d) strong rate acceleration by added nucleophiles. The activation parameters have been determined in two solvent systems. In contrast to 1 the secondary diazocompound CF 3 CN 2 CH 3 ( 2 ) follows the normal A ‐ S E 2 mechanism of rate‐determining proton transfer.
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