Study of Nitration and Oxidation in Oxynitrogen Systems.
Abstract
Our nitration results consistently demonstrate difficulties with the conventional nitronium ion scheme for mixed acid nitration. Ion molecule studies showed that the Wheland intermediate to aromatic nitration is not formed from the reaction NO(+2)+ArH, but rather from NO2+ArH+, a result consistent with electron transfer in aromatic nitration. In accord with this observation, we have found that the naphthalene radical cation, prepared independently and isolated as the crystalline salt and dissolved in nitromethane, reacts with NO2 in that medium to give nitronaphthalene with an alpha/beta ratio of about 50. In sulfuric acid media, we have measured directly the rates of nitronium ion formation and its rection with water over a range of acidities using 14N nmr spectroscopy. We also studied reactive aromatic hydrocarbons including mesitylene and p-xylene in fresh, NOx-free acid solution, but in the absence of NOx scavengers such as urea. In electrochemical studies in nitric acid, we have demonstrated the first electrochemical synthesis of TNT. The process takes place at room temperature in NO2/HNO3 media.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jun 01, 1983
- Accession Number
- ADA132742
Entities
People
- David S. Ross
- Ripudaman Malhotra
- Robert J. Schmitt
Organizations
- SRI International