<i>tert</i>‐Butyl Nitrite Mediated Nitro‐Nitratosation of Internal Alkenes
Bilal Ahmad Mir, Suresh Rajamanickam, Pakiza Begum, Bhisma K. Patel
Abstract
In an oxygen atmosphere tert ‐butyl nitrite (TBN) reacts with unsymmetrical internal benzylic alkenes giving nitro‐nitratosation product exclusively. The γ ‐diaryl‐substituted styrenes provided better yields compared to γ ‐alkyl‐aryl‐substituted styrenes. The higher yields for the former type of substrates is possibly dictated by the additional stability of benzylic radical due to the anchimeric assistance imparted by the γ ‐substituted phenyl ring. During oxidative nitration, the nitro (NO 2 ) group adds at the non‐benzylic site, whereas the nitrato group (ONO 2 ) is attached at the relatively stable benzylic position. Under similar reaction conditions, α,β ‐unsaturated carboxylic acids, afforded nitroalkenes as the sole product.