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- Title
An Experimentally Established Key Intermediate in Benzene Nitration with Mixed Acid.
- Authors
Koleva, Gergana; Galabov, Boris; Hadjieva, Boriana; Schaefer, Henry F.; Schleyer, Paul von R.
- Abstract
Experimental evidence is reported for the first intermediate in the classic SEAr reaction of benzene nitration with mixed acid. The UV/Vis spectroscopic investigation of the reaction showed an intense absorption at 320 nm (appearing as a band shoulder) arising from a reaction intermediate. Our theoretical modeling shows that the interaction between the two principal reactants with solvent (H2SO4) molecules significantly affects the structure of the initial complex. In this complex, a larger distance between the aromatic ring and nitronium ion precludes the possibility for electronic charge transfer from the benzene π-system to the electrophile. The computational modeling of the potential energy surface reveals that the reaction favors a stepwise mechanism with intermediate formation of π- and σ- (arenium ion) complexes.
- Subjects
INTERMEDIATES (Chemistry); NITRATION; BENZENE compound synthesis; ELECTROPHILIC substitution reactions; REACTION mechanisms (Chemistry)
- Publication
Angewandte Chemie, 2015, Vol 127, Issue 47, p14329
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201506959