Use of N‐chloro‐N‐methyl‐p‐toluenesulfonamide in N‐chlorination reactions. (20th May 2013)

• Record Type: Journal Article
• Authors: Pastoriza, Cristina; Antelo, Juan Manuel; Crugeiras, Juan
• Is Part Of: Journal of physical organic chemistry. Volume 26:Number 7(2013:Jul.)
• Page Start: 551
• Page End: 559
• Publication Date: 2013-05-20
• Subjects: N‐chlorination -- N‐chloro‐N‐methyl‐p‐toluenesulfonamide -- kinetics and mechanims -- free relationships -- N‐chloramines; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3127
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract : Second‐order rate constants (k2 ) were determined for the addition of ten nitrogenous organic compounds (benzylamine, 2, 2, 2‐trifluoethylamine chlorhidrate, methylamine chlorhidrate, glycine ethyl ester chlorhidrate, glycine, glycylglycine chlorhidrate, morpholine, pyperidine, pyperazine and dimethylamine) to the N‐chloro‐N‐methyl‐p‐toluenesulfonamide (NCNMPT) in the formation reaction of N‐chloramines in aqueous solution at 25 °C and ionic strength 0.5 M. The series of nucleophiles considered is structurally very varied and covers five pKa units. The kinetic behaviour is similar for all compounds, being the elementary step the transfer of chlorine from the NCNMPT molecule to the nitrogen of the free amino group. These reactions were found first order in both reagents. The values of the rate constants indicate that the more basic amines produce N‐chloramines more readily. Rate constants for thenucleophilic attack are shown to correlate with literature data for some of these nitrogenous organic compounds in their reaction with N‐methyl‐N‐nitroso‐p‐toluenesulfonamide. Both reactions involve that the rate determining step is the attack of nitrogenous compounds upon electrophilic centre (Cl or else NO group). NCNMPT is a particularly interesting substrate, for which has not hitherto been published kinetic information, that allows us to assess the efficiency and the competitiveness of this reaction and compare it with other agents with a Cl + atom. Copyright © 2013 John Wiley & Sons, Ltd. Abstract : N‐chloro‐N‐methyl‐p‐toluensulfonamide is a particularly chlorinating agent. The kinetic behaviour has been studied in the formation reaction of N‐chloramines using ten nitrogenous compounds.