Mechanism for the Uncatalyzed Cyclic Acetone-Peroxide Formation Reaction: An Experimental and Computational Study

Abstract

In this study, a mechanism for the uncatalyzed reaction between acetone and hydrogen peroxide is postulated. The reaction leads to the formation of the important homemade explosives collectively known as cyclic acetone peroxides (CAP). The proposed mechanistic scheme is based on Raman, GC-MS, and nuclear magnetic resonance measurements, and it is supported by ab initio density functional theory (DFT) calculations. The results demonstrate that the proposed mechanism for the uncatalyzed formation reaction of CAP occurs in three steps: monomer formation, polymerization of the 2-hydroperoxipropan-2-ol monomer, and cyclization. The temporal decay of the intensities of important assigned-bands is in excellent agreement with the proposed mechanism. Previous reports also confirm that the polymerization step is favored in comparison to other possible pathways.