Is Aromatic Nitration Spin Density Driven?

The mechanism of aromatic nitration is critically reviewed with particular emphasis on the paradox of the high positional selectivity of substitution in spite of low substrate selectivity. Early quantum chemical computations in the gas phase have suggested that the retention of positional selectivity at encounter-limited rates could be ascribed to the formation of a radical pair via an electron transfer step occurring before the formation of the Wheland intermediate, but calculations which account for the effects of solvent polarization and the presence of counterion do not support that point of view. Here we report a brief survey of the available experimental and theoretical data, adding a few more computations for better clarifying the role of electron transfer for regioselectivity.

Carbon-Coated Magnetic Iron Oxide Nanoparticles as Green Catalysts for Aromatic Nitration

Nitration of aromatic compounds is an important industrial process, which creates significant environmental pollution because of the harsh mineral acid catalysts. In this work, we report the synthesis and application of magnetic iron oxide nanoparticles as green catalysts for aromatic nitration. Magnetic iron oxide nanoparticles were synthesized by co-precipitation method and tested for nitration reactions on selected aromatic substrates, phenol, benzaldehyde, methylbenzoate, [Formula: see text]-cresol and [Formula: see text]-cresol. For the nitration reactions, sodium nitrite was used as the nitro-source and hydrogen peroxide as the oxidant. Effect of reaction conditions like, solvent, temperature and microwave treatment were studied. The magnetic nanoparticles were found to be more stable after coating with a carbon shell by a one-pot carbonization method. The reactions were fast with good product yield under solvent-free microwave conditions. The nano-catalyst was recovered magnetically after the reaction and reused for three batches of nitration, without significant loss in catalytic activity. The nanoparticles were characterized using scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), X-ray diffractometry (XRD) and FTIR spectroscopy.