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Kinetics and mechanism of chlorination of toluene and some substituted toluenes by chloramine‐T
Author(s) -
Radhakrishnamurti P. S.,
Pati Subas C.,
Dev B. R.
Publication year - 1982
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550141110
Subject(s) - toluene , chemistry , acetic acid , halogenation , medicinal chemistry , kinetics , chloramine t , organic chemistry , quantum mechanics , physics
The kinetics of chlorination of toluene, o ‐methyl toluene, p ‐methyl toluene, m ‐methyl toluene, and m ‐chlorotoluene by chloramine‐T(CAT) in aqueous acetic acid in the presence of HClO 4 have been studied. The reaction is first order with respect to [CAT] as well as [H + ]. The order with respect to the substrate is unity in the case of toluene and m ‐chlorotoluene, fractional in the case of o ‐methyl toluene and p ‐methyl toluene, and zero order in the case of m ‐methyl toluene. Nuclear halogenation has been observed with m ‐methyl toluene, while nuclear and side‐chain halogenation for p ‐methyl toluene and o ‐methyl toluene, and sidechain halogenation for toluene and m ‐chlorotoluene are the pathways. An increase in the proportion of acetic acid accelerates the rate. Added acetate ions inhibit the reaction, and added p ‐toluene sulfonamide causes a pronounced retardation. A mechanism involving AcO + HCl as the important electrophile is discussed.