Assessing Competitive Reaction Rates in the Nitration of 2-Methylbiphenyl, Biphenyl, and Toluene to Determine Steric Restriction in Resonance-Stabilized Planarization of the Carbocation Intermediates

Abstract

Electrophilic aromatic substitution (EAS) reactions have long been a fundamental addition to sophomore-level organic chemistry classes, allowing students the opportunity to explore the electron donating and withdrawing effects of electrons contained in the substituents of the aromatic reactant. In this paper we present preliminary findings on the nitration of methylated biphenyls using kinetic and regioselective assessments to analyze steric influences on the planarization of 2-methylbiphenyl after EAS nitration. Our preliminary findings show that nitration favors the methylated phenyl ring of 2-methylbiphenyl, indicating that the steric influence of the methyl group restricts planarization of the carbocation intermediate. Furthermore, a competition nitration reaction between biphenyl and toluene provides proof of concept for kinetic assessment of nitration rates that will eventually be applied to 2-methylbiphenyl; this competitive nitration showed that biphenyl nitrates 1.87 ± 0.61 (95% C.I.) times faster than toluene