Structure-activity considerations in kinetics and mechanism of chlorine exchange between chloramine-T and secondary amines.
To study the mechanism of N-chlorination of secondary amines by chloramine-T, the kinetics of the reactions of some aromatic-substituted analogues of N-chlorobenzenesulfonamide with various secondary amines were determined. The importance of amine basicity and reactivity of the N-Cl bond of the N-chlorobenzenesulfonamide was also assessed. The results indicate that a mechanism involving the un-ionized species of both reactants (i.e., a molecular mechanism), rather than an ionic mechanism, is operating and that the reaction most likely proceeds via a six-membered-ring transition state that incorporates a water molecule.
Dannan
H
H
College of Pharmacy, University of Kentucky, Lexington 40536-0082.
Hussain
A
A
Crooks
P A
PA
Dittert
L W
LW
D000465:Algorithms; D000588:Amines / Q000737:chemistry*; D000891:Anti-Infective Agents, Local / Q000494:pharmacology; D002700:Chloramines / Q000494:pharmacology*; D002713:Chlorine / Q000737:chemistry*; D004202:Disinfectants / Q000494:pharmacology*; D006863:Hydrogen-Ion Concentration; D066298:In Vitro Techniques; D007202:Indicators and Reagents / Q000494:pharmacology*; D007700:Kinetics; D013329:Structure-Activity Relationship; D014105:Tosyl Compounds
D000588:Amines; D000891:Anti-Infective Agents, Local; D002700:Chloramines; D004202:Disinfectants; D007202:Indicators and Reagents; D014105:Tosyl Compounds; C016300:chloramine-T; D002713:Chlorine