TY - JOUR
T1 - Parameters affecting mechanochemical nitration of aromatic precursors
AU - Vasudevan, Ashvin
AU - Schoenitz, Mirko
AU - Dreizin, Edward L.
N1 - Funding Information:
This work was supported by Strategic Environmental Research and Development Program (SERDP), award W912HQ19P0007 . Fruitful discussions and suggestions by Drs. N. Trivedi and L. Wingard of the Army Research Laboratory, Aberdeen Proving Grounds, MD, and Dr. E. Gauthier of the US Army, Picatinny Arsenal, NJ, are greatly appreciated.
Funding Information:
This work was supported by Strategic Environmental Research and Development Program (SERDP), award W912HQ19P0007. Fruitful discussions and suggestions by Drs. N. Trivedi and L. Wingard of the Army Research Laboratory, Aberdeen Proving Grounds, MD, and Dr. E. Gauthier of the US Army, Picatinny Arsenal, NJ, are greatly appreciated.
Publisher Copyright:
© 2021 Elsevier Ltd
PY - 2021/12/31
Y1 - 2021/12/31
N2 - Using MoO3 as catalyst and NaNO3 as nitronium source, aromatic precursors were nitrated in a planetary ball mill. Reaction times and nitrate/precursor molar ratios varied in the experiments. Nitration was observed with maximum yields approaching 80%. Product ratios of para to ortho isomers were consistently above 1, indicating reaction on the catalyst surface. Byproducts, including oxidation products and double nitration products, were observed. The product yield approached its theoretical maximum when the aromatic precursor was the limiting reactant; the yields remained well below their expected maxima when the limiting reactant was nitrate. Thus, the catalyst sites necessary to generate nitronium may be blocked by the excess of the aromatic precursor in such cases. Correlation of the reaction rates with characteristics of the precursors suggests the importance of both physical and chemical parameters. Factors affecting the reaction rate include the aromatic activation, basicity, enthalpy of vaporization, reaction enthalpies and viscosity.
AB - Using MoO3 as catalyst and NaNO3 as nitronium source, aromatic precursors were nitrated in a planetary ball mill. Reaction times and nitrate/precursor molar ratios varied in the experiments. Nitration was observed with maximum yields approaching 80%. Product ratios of para to ortho isomers were consistently above 1, indicating reaction on the catalyst surface. Byproducts, including oxidation products and double nitration products, were observed. The product yield approached its theoretical maximum when the aromatic precursor was the limiting reactant; the yields remained well below their expected maxima when the limiting reactant was nitrate. Thus, the catalyst sites necessary to generate nitronium may be blocked by the excess of the aromatic precursor in such cases. Correlation of the reaction rates with characteristics of the precursors suggests the importance of both physical and chemical parameters. Factors affecting the reaction rate include the aromatic activation, basicity, enthalpy of vaporization, reaction enthalpies and viscosity.
KW - Mechanochemistry
KW - Organic nitro-compounds
KW - Solvent-free nitration
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U2 - 10.1016/j.ces.2021.116906
DO - 10.1016/j.ces.2021.116906
M3 - Article
AN - SCOPUS:85109445400
SN - 0009-2509
VL - 246
JO - Chemical Engineering Science
JF - Chemical Engineering Science
M1 - 116906
ER -