Ian H. Pitman

Prediction of chlorine potentials of N-chlorinated organic molecules

Different linear free energy correlations have been found between the relative tendencies of (A) anions of imides and amides, and (B) secondary and tertiary amines, to accept a proton, or to accept a positive chlorine ion to yield a N-chloro-derivative. Using these relationships it should be possible to predict the chlorine potential of a N-chloro-compound when its structure and the acid dissociation constants of the N-chloro- and N-protonated derivatives are known.

Mechanism and thermodynamics of chlorine transfer among organohalogenating agents. Part IV. Chlorine potentials and rates of exchange

The relative abilities of organohalogenating agents, N-chloroquinuclidinium ion, N-chlorosuccinimide, N-chloro- and N-methyl-benzenesulphonamide, chloramine-T, dichloramine-T, dimethylchloramine, diethylchloramine, di-isopropylchloramine, dibutylchloramine, dipropylchloramine, methylbutylchloramine, N-chloropiperidine, and N-chloromorpholine to transfer their active chlorine to a suitable acceptor have been determined from both thermodynamic and kinetic standpoints. The secondary chloramines, although extremely weak bases, appear to react only in their protonated form. Of the tertiary N-chloro-ions, only N-chloroquinuclidinium ion and related bridge-head-nitrogen compounds are sufficiently stable to permit evaluation of their thermodynamic properties. The tendency to donate positive chlorine changes at pH 7 by a factor of 106 on going from diethylchloramine to N-chloroquinuclidinium ion. The work partly overlaps the classical studies of Soper and his co-workers although the experimental approaches and some of the results differ substantially.