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KINETICS AND ISOTOPE EFFECTS OF THE β-ELIMINATION REACTIONS OF 1,1-DICHLORO-2,2-BIS-(4-NITROPHENYL)-ETHANE PROMOTED BY PIPERIDINE, PYRROLIDINE AND QUINUCLIDINE BASES IN ACETONITRILE SOLVENT
Dworniczak, Miroslaw,Jarczewski, Arnold
, p. 599 - 604 (2007/10/02)
The kinetics of the reaction of 1,1-dichloro-2,2-bis-(4-nitrophenyl)ethane (I) with piperidine, pyrrolidine and quinuclidine bases in acetonitrile solvent are reported.The reaction is complex, leading to 1-amino-2,2-bis-(4-nitrophenyl)ethene (III) as the final product via the intermediate 1-chloro-2,2-bis-(4-nitrophenyl)ethene (II).The reaction shows a 100percent conversion of the substrate (I) to (II).The rate of reaction of I to II is several times faster than II to III, allowing for kinetic measurements of the initial step.The entropies of activation (ΔS*/J mol-1K-1) are negative and large (-184, -149, -145) for the reaction with piperidine, pyrrolidine and quinuclidine respectively.The free enthalpy of activation (ΔG*/kJ mol-1) are rather small, oscillating between 75-79 kJ mol-1.The kinetic isotope effects kH/kD fall between 6.8 and 7.6 at 20 deg C.The results obtained are interpreted in terms of E2H with a contribution of (E1cB)I mechanism.
