Hexamethylene triperoxide diamine

Jiang has reported a method of preparation of TeATeP using the reaction of acetone with hydrogen peroxide in presence of tin (II and IV) chloride or hydrochloric acid as the catalyst [100]. This method can however be disputed and according to our experience, normal TATP is formed [8]. 

The formation of tetraacetone tetraperoxide by ozonolysis (see reaction above) of tetramethylethene or isobutene has been described by Obinokov et al. [101]. These authors report a melting point of 61-65 °C. 

Hexamethylene triperoxide diamine (l,6-diaza-3,4,8,9,12,13-hexaoxabicyclo [4,4,4]tetradecane HMTD) was first prepared by Legler in 1885. He discovered it while working on the slow combustion of ether. He obtained a solid which, on treatment with ammonia, gave an explosive compound—HMTD [51, 102, 103]. The early history of this substance is described by Bagal [51]. 

The two nitrogen atoms in the HMTD molecule form an interesting and rare, totally planar, hybridization [104-106]. Two major hypotheses exist which try to explain this planarity an earlier one based on the steric effect [105] which has subsequently been superseded by a later one, based on an electronic effect [107]. The 3D model of HMTD molecule is shown in Fig. 10.15. 

HMTD forms colorless crystals (Fig. 10.16). Freshly prepared HMTD does not smell older samples acquire an unpleasant odor of rotten fish. Density of HMTD is mostly reported as 1.57 g cm [17, 58, 68, 103, 108] but X-ray investigation of 

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AN, ammonium nitrate HMTD, hexamethylene triperoxide diamine HMX, C4H8N8O8 NG, nitroglycerin PETN, pentaerythritol tetranitrate RDX, CsHgNgOg TATP, triacetone triperoxide ... 

The peroxide explosives TATP and hexamethylene triperoxide diamine (HMTD) have become popular with terrorists because they are easily prepared from readily obtainable ingredients, although the synthesis is fraught with danger (Figure 2). 

These are common abbreviations for the following TNT 2,4,6-trinitrotoluene AN ammonium nitrate PETN pentaerythritol tetranitrate HMX octahydro-l,3,5,7,-tetranitro-l,3,4,5-tetrazocine RDX hexahydro-l,3,5-trinitro-s-triazine HMTD hexamethylene triperoxide diamine TATP triacetone triperoxide. 

Oxley, J. C., J. L. Smith, H. Chen, and E. Cioffi. Decomposition of multi-peroxidic compounds Part II Hexamethylene triperoxide diamine (HMTD). Thermochem. Acta 388(1-2), 215-225 (2002). 

Inspired by the effective post-column photochemical conversion of hydroperoxides and peroxides to H2O2 just described, a method was developed for trace analysis of peroxide explosives, such as triacetone triperoxide (251) and hexamethylene triperoxide diamine (252). These are powerful explosives with no commercial or military applications because... 

Heteropoly acid, tungstate-based, 496, 497 Hexacoordinate silyl peroxides, 808-10 , -Hexa-2,4-diene, photooxidation, 254-5 Hexamethyldisiloxane, oxidation, 806-7 Hexamethylene triperoxide diamine (HMTD) enthalpy of formation, 166 explosive, 707-8... 

HMHP see Hydroxymethyl hydroperoxide HMTD (hexamethylene triperoxide diamine), 166, 707-8... 

J.C. Oxley, J.L.Smith, H. Chen, E. Cioffi, Decomposition of Multi-Peroxidic Compounds Part II Hexamethylene Triperoxide Diamine (HMTD) Thermochim. Acta, 388 (2002) 215-225. 

Explosives that were detectable included TNT, dinitrotoluene (DNT), RDX, HMX, PETN, EGDN, NG, Tetryl, ammonium nitrate fuel oil (ANFO), triacetone triperoxide (TATP), and hexamethylene triperoxide diamine (HMTD). Analysis time is less than 15 s. Figure 6 shows schematically how such a portal works ... 

Fig. 15. (a) Differential mobility spectra of triacetone triperoxide (TATP) in air at different concentrations. Product ions can only be detected in the positive mode, negative product ions cannot be observed, (b) Differential mobility spectra of hexamethylene triperoxide diamine (HMTD) in air at different concentrations. Product ions can be detected both in positive and negative polarity. The additional peak in the positive mode could be attributed to a co-eluting solvent, acetonitrile (ACN). 

Fig. 16. Gas chromatography-differential mobility spectrometry (GC-(DMS) topographic plot [retention time (v-axis), compensation voltage (y-axis), intensity (z-axis)] of a mixture of seven explosives (lOOng in acetonitrile) hexamethylene triperoxide diamine (HMTD), ethylene glycol dinitrate (EGDN), triacetone triperoxide (TATP), 2-mononitrotoluene (2-MNT), 4-MNT, 2,4-dinitrotoluene (2,4-DNT), and 2,4,6-trinitrotoluene (TNT).

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

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). 

Hexamethylene triperoxide diamine (HMTD) was one of the explosive compounds identified at a property in Escondido, California, in November 2010, which led to the house being intentionally burned to the ground by authorities. Each atom is equivalent to the other atoms of same atomic number (so all six carbons are equivalent, both nitrogens, and so on). Assign HMTD to its point group. 

Fig. 10.15 HMTD geometry and atom labeling [105]. Reprinted with permission from A. Wierzbicki and E. Cioffi, Density Functional Theory Studies of Hexamethylene Triperoxide Diamine, J. Phys. Chem. A 1999, 103, 8890-8894. Copyright (1999) American Chemical Society...

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