Potassium Periodate/NaNO₂ /KHSO₄ -Mediated Nitration of Aromatic Compounds and Kinetic Study of Nitration of Phenols in Aqueous Acetonitrile

Abstract

Synthesis and kinetics of potassium periodate(KIO4)/NaNO2/KHSO4)‐initiated nitration of aromatic compounds have been studied in aqueous acetonitrile medium. Synthesis of nitroaromatic compounds is achieved under conventional and solvent‐free microwave conditions. Reaction times in microwave‐assisted reaction are comparatively less than in conventional reaction. The reaction kinetics for the nitration of phenols in aqueous bisulfate and acetonitrile medium indicated first‐order dependence on [phenol], [NaNO2], and [KIO4]. An increase in [KHSO4] accelerated the rate of nitration under otherwise similar conditions. The rate of nitration increased in the solvent of high dielectric media (solvents with high dielectric constant (D)). Observed results were in accordance with Amis and Kirkwood plots [log k′ vs. (1/D) and [(D − 1)/(2D + 1)]. These observations probably indicate the participation of anionic species and molecular or (dipolar) species in the rate‐determining step. In addition, the plots of (log k′) versus volume% of organic solvent were also linear, which probably indicate the importance of both electrostatic and nonelectrostatic forces, solvent–solute interactions during nitration of phenols. Reaction rates accelerated with the introduction of electron‐donating groups and retarded with electron‐withdrawing groups, but results could not be quantitatively correlated with Hammett's equation and depicted deviations from linearity. These deviations could probably be attributed to cumulative effects arising inductive, resonance, and steric effects. Leffler's plot (ΔH# vs. ΔS#) was found linear indicating the compensation (cumulative) effect of both enthalpy and entropy parameters in controlling the mechanism of nitration.

Synthetic Protocols for Aromatic Nitration: A Review

“…The plausible mechanism given by authors shows that nitrile reduces diprotonated periodate and from nitronium iodate through decreasing oxidation state of iodine +7 to +5. And then In the presence of free hydrogen nitronium iodate converts to iodate ions and releases NO 2 + ions which responsible for the nitration of phenols [44] …”

Trichloroisocyanuric acid and NaNO2 mediated nitration of indoles under acid-free and Vilsmeier–Haack conditions: synthesis and kinetic study

“…Mukherjee and Boshaff [18] explored that nitroimidazoles could be effectively used for the treatment of TB. During the past two decades our research group is also actively involved to achieve nitration using eco-friendly reagents and catalysts [19][20][21][22][23][24][25][26][27][28][29].…”

Silica-supported HClO4 and KHSO4 as reusable green catalysts for sulfonation of aromatic compounds under solvent-free conditions

“…In recent past, several aluminium and silica-supported acid catalysts are developed to overcome these issues, which afforded better yields and productivity in comparison to conventional protocols [14][15][16][17][18][19][20][21][22][23][24], because solid supported catalysts possess high surface, long catalytic life, environment-friendliness, and provide good to excellent yields with simple work-up procedure.…”

“…We have recently explored silica supported HClO4 and KHSO4 materials as reusable green catalysts for thiocyanation of aromatic compounds under conventional and solvent-free microwave assisted conditions [24]. Stimulated by the noteworthy advantages of silica-supported catalysts, we have embarked on exploring silica supported HClO4 and KHSO4 as an efficient catalysts for sulfonation of aromatic compounds in the present study (Schem 1).…”

“…Microwave-assisted (MWA) reactions were performed in a bench mate model microwave oven (CEM-908010, bench mate model, 300W laboratory microwave reactor) was used in this study. Method of the preparation, and characterization of Silica supported catalysts (SiO2/KHSO4 and SiO2/HClO4) is the same as reported in our recent publication[24].…”