Efficient synthesis of N-(chloromethyl)nitramines via TiCl4-catalyzed chlorodeacetoxylation

Abstract

The nitramino group is an important motif in energetic compounds, positively influencing the oxygen and nitrogen content, density and enthalpy of formation. Herein, a simple, mild and general procedure has been developed for the preparation of diverse N-(chloromethyl)nitramine building blocks from readily available N-(acetoxymethyl)nitramines via a TiCl₄-catalyzed chlorodeacetoxylation with SOCl₂. This new protocol allows the conversion of both mono- and di(acetoxymethyl) precursors that contain one to four nitramino groups into functionalized chloromethyl compounds in excellent yields.