Electrochemical Nitration with Nitrite
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Updated: Oct 18, 2025

Measuring Nitrite and Nitrate, Metabolites in the Nitric Oxide Pathway, in Biological Materials using the Chemiluminescence Method
Published on: December 25, 2016
Stephan P Blum1, Christean Nickel1, Lukas Schäffer1
1Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Abstract:
Aromatic nitration has tremendous importance in organic chemistry as nitroaromatic compounds serve as versatile building blocks. This study represents the electrochemical aromatic nitration with NBu4 NO2 , which serves a dual role as supporting electrolyte and as a safe, readily available, and easy-to-handle nitro source. Stoichiometric amounts of 1,1,1-3,3,3-hexafluoroisopropan-2-ol (HFIP) in MeCN significantly increase the yield by solvent control. The reaction mechanism is based on electrochemical oxidation of nitrite to NO2 , which initiates the nitration reaction in a divided electrolysis cell with inexpensive graphite electrodes. Overall, the reaction is demonstrated for 20 examples with yields of up to 88 %. Scalability is demonstrated by a 13-fold scale-up.
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