Mechanochemical nitration of arenes and alcohols using a bench-stable organic nitrating reagent

Abstract

The installation of a nitro group, essential for synthesizing valuable nitrated compounds, is traditionally associated with harsh reaction conditions, hazardous reagents, and significant environmental concerns. Recent advancements in sustainable nitration methodologies have led to the development of environmentally benign, mild, and non-acidic nitrating reagents, which are often derived from an organic scaffold and can be recycled after the completion of the process. In this study, we demonstrate the practical application of saccharin-derived reagents in mechanochemical electrophilic nitration, utilizing vibratory ball milling under LAG (Liquid-Assisted Grinding) conditions to efficiently functionalize a wide array of alcohols and arenes. This method decreases solvent usage while preserving high selectivity and reactivity, enhancing green chemistry metrics, and fostering greater sustainability in nitration protocols.