TITLE:
Solid-Phase Aromatic Nitration with Mg(NO3)2 on Silica Gel
AUTHORS:
Tomoko Matsumoto, Ayaka Yamauchi, Jun Ishikawa, Guan-Hong Jin, Jin Matsumoto, Yoshiyuki Fueda, Masahide Yasuda
KEYWORDS:
Aromatic Nitration, Silica Gel, Mg(NO3)2, Solid State
JOURNAL NAME:
International Journal of Organic Chemistry,
Vol.7 No.1,
December
27,
2016
ABSTRACT: Nitroaromatics are usually prepared using a mixed acid of nitric acid with strong acids. However, the use of strong acids caused dangerous work-up and the disposal of large amounts of acid-waste. Therefore, much effort has been made on the improvement of nitration process without strong acids. We examined solid-phase aromatic nitration with Mg(NO3)2 on silica gel in order to establish the nitration process without strong acids. The nitration of 1,2- and 1,3-, 1,4-dimethoxybenzenes and 4-methylanisole with Mg(NO3)2 proceeded by heating on silica gel at 150°C for 4 - 5 h to produce the nitroaromatics. The nitration of 1,3,5-trimethoxybenzene produced the nitrated dimer, 2,4,6,2’, 4’,6’-hexamethoxy-3-nitrobiphenyl, which was not isolated in other solid-phase nitration. In the cases of naphthalene derivatives, the α-nitrated compounds were obtained. In the cases of p-cresol and 2-naphthol, the esterification occurred at the hydroxyl group to give 4-tolyl nitrate and 2-naphthyl nitrate, respectively. It is synthetic interest to note that nitrate esters were isolated in solid phase. Thus Mg(NO3)2-SiO2 composite was mild reagent for solid-phase nitration. Acidity of Mg(NO3)2-SiO2 composite was determined to be pH 0.96 by the measurement of absorption spectra on a micro spectrophotometer using meso-tetra(p-cyanophenyl)porphyrin as a pH-indicator. Mg(NO3)2-SiO2 composite made acidic conditions. Therefore, it was suggested that Mg(NO3)2 reacted with proton on silica gel to form the NO+2. Thus, electron-rich aromatic hydrocarbons led the efficient nitration through electrophilic attack of NO+2. After the nitration, acidic Mg(NO3)2-SiO2 composite could be turned into neutrality by exposing wet conditions and disposed safely since the composite did not involve harmful elements. Thus the solid-phase nitration using Mg(NO3)2-SiO2 composite will provide safety and environmentally conscious chemical process.