283-66-9Relevant articles and documents
Density functional theory and X-ray investigations of P- and M-hexamethylene triperoxide diamine and its dialdehyde derivative
Wierzbicki, Andrzej,Salter, E. Alan,Cioffi, Eugene A.,Stevens, Edwin D.
, p. 8763 - 8768 (2001)
Recently, we carried out a density functional theory B3LYP/6-31+G(d) study of hexamethylene triperoxide diamine (HMTD) in order to elucidate the unusual, nearly planar, sp2 hybridization of the two bridgehead nitrogen atoms, each bonded to the three CH2 groups. We postulated that extended bonding orbitals between peroxide oxygens results in charge delocalization which decreases lone-pair repulsion and compensates the energy loss due to the sp3 to sp2 hybridization change on the nitrogen atoms. We have reexamined the crystal structure of HMTD by performing low-temperature, single-crystal X-ray studies, and we have determined that the unit cell contains a 50-50 racemic mixture of enantiomeric forms of HMTD, showing disorder about the mirror plane. At the low temperature, all hydrogen atoms were located and resolved, which was not previously possible. We have also crystallized and performed low-temperature X-ray analysis of a never previously reported dialdehyde form of HMTD, tetramethylene diperoxide diamine dialdehyde (TMDDD), which reveals enantiomers present in the unit cell without disorder. B3LYP density functional theory studies of HMTD and TMDDD are presented, as well as a transition state investigation of possible thermal interconversion of the HMTD enantiomers.
Helical chirality in hexamethylene triperoxide diamine
Guo, Chunlei,Persons, John,Harbison, Gerard S.
, p. 832 - 837 (2006)
The primary explosive hexamethylenetriperoxide diamine has previously been found to exist in the solid state as a racemic mixture of helically chiral, threefold symmetric enantiomers; another enantiomeric pair of low-energy conformers has been predicted, but has never been observed. We show by solution 2D NMR at 14 T, in achiral solution and by addition of chiral shift reagents, that all four optically isomeric conformers coexist at slow equilibrium on the NMR timescale at room temperature, and can be observed. Calculations of the 1H and 13C NMR chemical shifts using gauge-including atomic orbital methods are in excellent agreement with experiment; thermochemical calculation of the free energies in solution are in somewhat worse agreement, but correctly predict the relative stability of the conformers. Analysis of the effects of chiral shift reagents on the NMR spectra suggests that discrimination between chiral isomers is primarily around the molecular equator, around which the enantiomeric gauche O-O linkages are arrayed. Copyright
Differentiation among peroxide explosives with an optoelectronic nose
Li, Zheng,Bassett, Will P.,Askim, Jon R.,Suslick, Kenneth S.
supporting information, p. 15312 - 15315 (2015/10/20)
Forensic identification of batches of homemade explosives (HME) poses a difficult analytical challenge. Differentiation among peroxide explosives is reported herein using a colorimetric sensor array and handheld scanner with a field-appropriate sampling protocol. Clear discrimination was demonstrated among twelve peroxide samples prepared from different reagents, with a classification accuracy >98%.
