Kinetics and calculations in the NO3-promoted gas phase nitration of phenol with NO2

ORGN 93

Guido Galliani, g.galliani@chorisis.it1, Ezio Bolzacchini, Ezio.Bolzacchini@unimi.it2, Maurizio Bruschi, maurizio.bruschi@unimib.it2, Marco Orlandi2, Bruno Rindone, Bruno.Rindone@unimib.it2, and Jens Hjorth3. (1) Chorisis srl, Mariano Comense, Italy, (2) Department of Environmental Sciences, University of Milano-Bicocca, Piazza della Scienza, 1, Milano, I-20126, Italy, (3) Environment Institute, JRC, Ispra, I-21020, Italy
Product studies, kinetic isotope effect measurements, linear free energy relationships and calculations have been used to study the NO3-promoted nitration of phenol in presence of NO2. The competition between a rate-determining hydrogen abstraction of NO3 to give a phenoxy radical and nitric acid and and of a rate-determining addition-elimination pathway (ADD) has been evaluated. The NO3-promoted nitration of phenol in presence of NO2 occurs mostly via a rate-determining ADD mechanism and the stereocontrolled elimination of nitric acid has an important role in driving the reaction toward the ortho-nitration. A kinetic analysis suggests reasons for the dependence of the ratio ortho:para-nitration from the initial concentration of reactants. These observations may be useful for modelling the chemistry in the tropospheric gas phase.
 

Process R&D, Physical Organic Chemistry, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Sunday, March 25, 2007 Hyatt Regency Chicago -- Riverside Center, Poster

Division of Organic Chemistry

The 233rd ACS National Meeting, Chicago, IL, March 25-29, 2007