Energetic Materials Trends in 5- and 6-Membered Cyclic Peroxides Containing Hydroperoxy and Hydroxy Substituents

Ten peroxide compounds based upon the 3,6‐di(hydroperoxy)‐1,2‐dioxane, 2‐hydroxy‐6‐hydroperoxy‐1,2‐dioxane, 3,5‐di(hydroperoxy)‐1,2‐dioxolane, and 3‐hydroxy‐5‐hydroperoxy‐1,2‐dioxolane skeletons have been synthesized, structurally characterized, and fully evaluated for their energetic materials properties. The solid‐state structures of these compounds are dominated by hydrogen bonding interactions involving the hydroperoxy and hydroxy groups. Energetic materials testing shows that most of the compounds are highly sensitive toward impact and friction, with similar properties to highly sensitive peroxides such as triacetone triperoxide. 3,5‐Diethyl‐5‐hydroperoxy‐1,2‐dioxolan‐3‐ol (3b) and 3,5‐dimethyl‐5‐hydroperoxy‐1,2‐dioxolan‐3‐ol (5b) have lower impact and friction sensitivities than the other compounds, with values that are appropriate for use as primary explosives. Oxygen‐rich 5‐ and six‐membered cyclic peroxides have been prepared and fully characterized, including by X‐ray crystallography, electronic structure calculations, and detailed energetic materials testing. Most compounds are highly sensitive toward impact and friction, but two compounds where X = OH have reduced sensitivities.