| Abstract
| - A prolonged search involving several dozen phenols, each in numerous solvents, for an ArOH/2,2-diphenyl-1-picrylhydrazyl (dpph•) reaction that is first-order in ArOH but zero-order in dpph• hasreached a successful conclusion. These unusual kinetics are followed by 2,2‘-methylene-bis(4-methyl-6-tert-butylphenol), BIS, in five solvents (acetonitrile, benzonitrile, acetone, cyclohexanone, andDMSO). In 15 other solvents the reactions were first-order in both BIS and dpph• (i.e., the reactionsfollowed “normal” kinetics). The zero-order kinetics indicate that in the five named solvents theBIS/dpph• reaction occurs by sequential proton loss electron transfer (SPLET). This mechanism isnot uncommon for ArOH/dpph• reactions in solvents that support ionization, and normal kineticshave always been observed previously (see Litwinienko, G.; Ingold, K. U. J. Org. Chem. 2003, 68,3433 and Litwinienko, G.; Ingold, K. U. J. Org. Chem. 2004, 69, 5888). The zero-order kineticsfound for the BIS/dpph• reaction in five solvents, S, imply that BIS ionization has become therate-determining step (rds, rate constants 0.20−3.3 s-1) in the SPLET reaction sequence: S + HOAr⇌ S− HOArSH+ + -OArSH+ + •OAr + dpph- → S + •OAr + dpph-H, where ArOH =BIS. Some properties specific to BIS that may be relevant to its relatively slow ionization in thefive solvents are considered.
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