Cyclic acetone peroxide explosives

Cyclic acetone peroxides are an important class of home-made explosives, being easily prepared from household materials, but also highly unstable. An experimental and DFT investigation of the uncatalysed reaction of acetone and hydrogen peroxide has identified key steps (i) formation of the monomer, 2-hydroperoxipropan-2-ol, HO-CMe2-0-0-H (ii) polymerization and (iii) cyclization. DFT-generated reaction profiles match well with GC-MS, Raman and NMR observations over time. 

Contact with many organic compounds can lead to immediate fires or violent explosions (consult Bretherick for references and examples). Hydrogen peroxide reacts with certain organic functional groups (ethers, acetals, etc.) to form peroxides, which may explode upon concentration. Reaction with acetone generates explosive cyclic dimeric and trimeric peroxides. Explosions may also occur on exposure of hydrogen peroxide to metals such as sodium, potassium, magnesium, copper, iron, and nickel. 

The effect of the nitric acid/hydrogen peroxide mixture on acetone when it is hot gives rise to an explosive oxidation, especially when the medium is confined. This situation also applies to a large number of ketones, and in particular, cyclic ketones. Cyclic di- and triperoxides form compounds that detonate, if there is no strict and very delicate thermal control. Accidents have been reported with butanone, 3-pentanone, cyclopentanone, cyclohexanone and methylcyclo-hexanones. 

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