NUCLEOPHILIC ADDITION TO OLEFINS. 8. 1 ADDITION OF PIPERIDINE, MORPHOLINE, AND n-BUTYLAMINE TO alpha -CYANO-4-NITROSTILBENE AND alpha -CYANO-2,4-DINITROSTILBENE. KINETICS AND EQUILIBRIA IN 50% Me2SO-50% WATER.

Article abstract of DOI:10.1021/ja00351a038

Amines add rapidly to the double bond of alpha -cyano-4-nitrostilbene (1-NO//2) and alpha -cyano-2,4-dinitrostilbene (1-(NO//2)//2) to form a zwitterionic Michael adduct, T//A** plus or minus , which loses a proton to form the anionic adduct T//A** minus . With n-butylamine and piperidine nucleophilic attack is rate limiting under all reaction conditions. With morpholine deprotonation is rate limiting at low amine concentration and low pH, but nucleophilic attack becomes rate limiting at high concentration or high pH. Rate and equilibrium constants for nucleophilic addition could be measured or estimated for all reactions, and, for the morpholine adducts, rate constants for proton transfer involving H//3O** plus , OH** minus , the solvent, morpholine, and several buffers could also be evaluated.