Diacetone Diperoxide

The molecule of diacetone diperoxide exhibits chain conformation in the solid state (see Fig. 10.1) [13,14]. These conformers are bonded by intermolecular hydrogen bonds which result in the formation of layers of molecules as shown in Fig. 10.2. This picture further clearly shows that all of the oxygen atoms of DADP are involved in hydrogen bond bridges [13], 

Diacetone diperoxide forms colorless crystals (see Fig. 10.3) with crystal density 1.33 g cm (X-ray) [13, 14] and melting point published mostly in the range 130-132 °C [11, 15-18]. 

DADP is a very volatile substance vapor pressure of DADP is 17.7 Pa at 25 °C (determined by gas chromatography). The Qapeyron equation, which describes dependence of vapor pressure (F in Pa) on temperature (T in K), is  

DADP is a more volatile substance than TATP [19], Its vapor pressure is, according to Oxley, about 2.6 times higher than that of TATP at the same temperature. The reason is most likely due to a lower molecular weight. The heat of sublimation of DADP is 81.9 kJ moP (calculated from the Clapeyron 

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Two forms of acetone peroxides are known to exist a dimer called diacetone diperoxide (DADP) and a trimer called triacetone triperoxide (TATP). Figure 3.4 displays the chemical structures of each. 

Acetone peroxides 1 A41—A45 diacetone diperoxide 1 A41—A42 triacetone triperoxide 1 A42—A45... 

Diacetin. See under Acetins A31-R Diacetone Diperoxide. See under Acetone Peroxides A41-R... 

Both X-ray crystallography and electronic structure calculations using the cc-pVDZ basis set at the DFT B3LYP level have been employed to study the explosive properties of triacetone triperoxide (TATP) and diacetone diperoxide (DADP).32 The thermal decomposition pathway of TATP has been investigated by a series of calculations that identified transition states, intermediates, and the final products. Calculations predict that the explosion of TATP is not a thermochemically highly favoured event. It rather involves entropy burst, which is the result of formation of one ozone and three acetone molecules from every molecule of TATP in the solid state. 

Fig. 1.14 Molecular structures of triacetone triperoxide (TATP), hexamethylene triperoxide diamine (HMTD), methyl ethyl ketone peroxide (MEKP) and diacetone diperoxide (DADP).

Hexaoxonane 11 underwent a slow ring narrowing in methylene chloride or chloroform in the presence of /i-toluenesulfonic acid (PTSA) to yield 60% of diacetone diperoxide <2005JA1146>. 

Diacetone Diperoxide. See Acetoneperoxide, Dimeric or Diacetone Diperoxide in Vol 1, p A41-R... 

Peroxide-based explosives, such as TATP, diacetone diperoxide (DADP), and hexamethylene triperoxide diamine (MHTD) can be detected using HPLC-DAD at 214 nm (see Figmes 11.5 and 11.6). Successful LC-MS/MS of explosives has been reported, as has the use of ion mobility and liquid chromatography with amperometric detection (Vigneau and Machuron-Mandard 2009 Hilmi et al. 1999 Ou et al. 2009 Meng et al. 2008). 

Fig. 12.14 Raman and infiared vibrational frequency spectium of diacetone diperoxide (pink line), triacetone ttiperoxide (blue line), graphene ribbon (red line) diacetone diperoxide adsorbed in graphene (green) and triacetone triperoxide adsorbed on graphene (gray line). Vibrational modes generated in the low region of the spectrum (below 50 cm ) (Reprinted from Ref. [38] with kind permission of The American Institute of Physics)...

Oxley, J.C., Smith, J.L., Luo, W., Brady, J. Determining the vapOT pressure of diacetone diperoxide (DADP) and hexamethylene triperoxide diamine (HMTD). Propellants Explosives Pyrotechnics 34,539-543 (2009)... 

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