7025-90-3Relevant academic research and scientific papers
Kinetics of the decay reactions of the N,N-dimethyl-p-toluidine cation radical in acetonitrile. Acid-base interaction to promote the CH2-CH2 bonding
Goto, Masashi,Park, Hyun,Otsuka, Koji,Oyama, Munetaka
, p. 8103 - 8108 (2002)
The decay reaction of N,N-dimethyl-p-toluidine (DMT) cation radical (DMT?+) in acetonitrile (AN) was analyzed using an electron-transfer stopped-flow (ETSF) method. In the ETSF method, DMT?+ is generated by mixing AN solutions of DMT and tris(p-bromophenyl) amine cation radical (TBPA?+). When DMT?+ was generated quantitatively without DMT via 1:1 mixing of DMT and TBPA?+, it was found that DMT?+ was fairly stable in AN. On the other hand, when DMT remained with DMT?+ under the control of the mixing ratio of DMT/TBPA?+ (> 1), the neutral DMT was found to promote the decay reaction of DMT?+. From the determined rate law, -d[DMT?+]/dt = k [DMT?+] [DMT] (k = 6.5 × 102 M-1 s-1), the initial acid-base reaction between DMT?+ and DMT was clarified to be the rate determining step. The acid-base interaction was also confirmed by observing the decay reaction of DMT?+ in the presence of pyridine derivatives. The identical rate law, which indicates the rate-determining acid-base interaction, was obtained for eight pyridine derivatives examined, though the final product was different from the case of DMT. The ETSF method has permitted the straightforward analysis and given a definite kinetic conclusion concerning the acid-base reaction between DMT?+ and DMT.
