The low efficiency of p-toluenesulfonyl chloride (TsCI) initiator for the polymerization of methyl methacrylate (MMA), when used in conjunction with N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA) and CuBr under atom transfer radical polymerization (ATRP) conditions was investigated. A major by-product in the formation of poly(methyl methacrylate) was identified as N,N-dimethyl-p-toluenesulfonamide (5) and accounted for approximately half of the initiator. Compound 5 was shown to form by the direct reaction of PMDETA and TsCl. In a model experiment equimolar amounts of TsCl, PMDETA and CuBr reacted at 80 degrees C in p-xylene resulted in the formation of 5 and two other unsaturated suffones 2-methyl-3-[(4-methylphenyl)sulfonyl]-2-propenoic acid methyl ester (6) and 2-[[4-methylphenyl)sulfonyl]methyl]-2-propenoic acid methyl ester (7), formed by the dehydrohalogenation and subsequent isomerization of an intermediate chloro-adduct, 1-(4-methylbenzenesulfonyl)-2-chloro-2-(methyl)methyl propionate (2). Molecular modeling predicted the unsaturated sulfone 7 was thermodynamically more stable than the higher conjugated sulfone 6 and this was confirmed by the isomerization of 6 to 7 at room temperature under mild basic conditions. The absence of 6 and 7 in the polymerization of MMA under ATRP conditions showed that in the early stages of polymerization in the presence of excess MMA, the intermediate chloro-adduct 2 is not formed. (c) 2005 Elsevier Ltd. All rights reserved.