Absence of abnormal carbon-14 isotope effect in the alkaline degradation of NN-dimethyl-o-toluidine [14C]methiodide

Author(s):  
J. McKenna ◽  
J. M. McKenna ◽  
J. M. Stuart

Di- tert . butyl peroxide labelled with carbon-14 has been used to initiate the polymerization of styrene, and the resulting polymers have been analyzed for fragments derived from the peroxide. Polymers prepared in benzene solution contain both tert . butoxy and methyl end-groups, the proportions depending upon the conditions prevailing during polymerization; except at low concentrations of styrene and high temperatures, initiation is chiefly by the tert . butoxy radical giving polymer molecules with ether end-groups. In some diluents, initiation is largely by an indirect process in which the primary radicals abstract hydrogen from the diluent. There is an isotope effect in the dissociation of the tert . butoxy radical; introduction of carbon-14 into the radical reduces by about 7% the velocity constant for dissociation to give acetone at 130°C. Allowance must be made for this effect when using the labelled peroxide as a source of tert . butoxy radicals to be used in competitive studies of the reactivities of substances towards these radicals.


1967 ◽  
Vol 32 (12) ◽  
pp. 4116-4116
Author(s):  
Ernst M. Hodnett ◽  
William J. Dunn
Keyword(s):  

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