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tert ‐Butyl Nitrite Mediated Nitro‐Nitratosation of Internal Alkenes
Author(s) -
Mir Bilal Ahmad,
Rajamanickam Suresh,
Begum Pakiza,
Patel Bhisma K.
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202000149
Subject(s) - chemistry , nitro , nitration , nitrite , medicinal chemistry , alkyl , aryl , oxygen , nitro compound , ring (chemistry) , organic chemistry , nitrate
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.