TY - GEN
T1 - Nitration mechanisms of anisole during gamma irradiation of aqueous nitrite and nitrate solutions
AU - Elias, Gracy
AU - Mincher, Bruce J.
AU - Mezyk, Stephen P.
AU - Cullen, Thomas D.
AU - Martin, Leigh R.
PY - 2010/10/15
Y1 - 2010/10/15
N2 - The nitration of aromatic compounds in the condensed phase is of interest to nuclear waste treatment applications. This chapter discusses our investigation of radiolytic aromatic nitration mechanisms in the condensed phase toward understanding the nitration products created during nuclear fuel reprocessing. The nitration reactions of anisole, a model aromatic compound, were studied in ?-irradiated acidic nitrate, neutral nitrate, and neutral nitrite solutions. The nitrated anisole product distributions were the same with and without radiation in acidic solution, although more products were formed with radiation. In the irradiated acidic condensed phase, radiation-enhanced nitrous acid-catalyzed nitrosonium ion electrophilic aromatic substitution followed by oxidation reactions dominated over radical addition reactions. Neutral nitrate anisole solutions were dominated by mixed nitrosonium/nitronium ion electrophilic aromatic substitution reactions, but with lower product yields. Irradiation of neutral nitrite anisole solution resulted in a statistical substitution pattern for nitroanisole products, suggesting non-electrophilic free radical reactions involving the .NO2 radical.
AB - The nitration of aromatic compounds in the condensed phase is of interest to nuclear waste treatment applications. This chapter discusses our investigation of radiolytic aromatic nitration mechanisms in the condensed phase toward understanding the nitration products created during nuclear fuel reprocessing. The nitration reactions of anisole, a model aromatic compound, were studied in ?-irradiated acidic nitrate, neutral nitrate, and neutral nitrite solutions. The nitrated anisole product distributions were the same with and without radiation in acidic solution, although more products were formed with radiation. In the irradiated acidic condensed phase, radiation-enhanced nitrous acid-catalyzed nitrosonium ion electrophilic aromatic substitution followed by oxidation reactions dominated over radical addition reactions. Neutral nitrate anisole solutions were dominated by mixed nitrosonium/nitronium ion electrophilic aromatic substitution reactions, but with lower product yields. Irradiation of neutral nitrite anisole solution resulted in a statistical substitution pattern for nitroanisole products, suggesting non-electrophilic free radical reactions involving the .NO2 radical.
UR - http://www.scopus.com/inward/record.url?scp=84905500839&partnerID=8YFLogxK
U2 - 10.1021/bk-2010-1046.ch017
DO - 10.1021/bk-2010-1046.ch017
M3 - Conference contribution
AN - SCOPUS:84905500839
SN - 9780841225855
T3 - ACS Symposium Series
SP - 205
EP - 214
BT - Nuclear Energy and the Environment
PB - American Chemical Society
ER -
