Organic and Biomolecular Chemistry p. 3781 - 3789 (2019)
Update date:2022-08-03
Topics:
Shernyukov, Andrey V.
Genaev, Alexander M.
Salnikov, George E.
Shubin, Vyacheslav G.
Rzepa, Henry S.
The kinetics and mechanism of concurrent bromo-de-protonation and bromo-de-tert-butylation of 1,3,5-tri-tert-butylbenzene at different bromine concentrations were studied experimentally and theoretically. Both reactions have high order in bromine (experimental kinetic orders ~5 and ~7, respectively). According to quantum chemical DFT calculations, such high reaction orders are caused by participation of clustered polybromide anions Br2n?1- in transition states. Bromo-de-tert-butylation has a higher order due to its bigger reaction center demanding clusters of extended size. A significant primary deuterium kinetic isotope effect (KIE) for bromo-de-protonation is measured indicating proton removal is rate limiting, as confirmed by computed DFT models. The latter predict a larger value for the KIE than measured and possible explanations for this are discussed.
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