Acetone peroxide

Acetone peroxide


[Cyclic dimer and trimer examples]
Names
IUPAC names
3,3-Dimethyl-1,2-dioxacyclopropane
(monomer)
3,3,6,6-Tetramethyl-1,2,4,5-tetraoxane
(dimer)
3,3,6,6,9,9-Hexamethyl-1,2,4,
5,7,8-hexaoxacyclononane
(trimer)
3,3,6,6,9,9,12,12-Octamethyl-1,2,4,
5,7,8,10,11-octaoxacyclododecane
(tetramer)
Other names
Triacetone Triperoxide
Peroxyacetone
Mother of Satan
Identifiers
17088-37-8 N
ChemSpider 3582942 YesY
Jmol 3D model dimer: Interactive image
trimer: Interactive image
PubChem 4380970
Properties
C6H12O4 (dimer)
C9H18O6 (trimer)
C12H24O8 (tetramer)
Molar mass 148.157 g/mol (dimer)
222.24 g/mol (trimer)
Appearance White crystalline solid
Melting point 91 °C (196 °F; 364 K)
Boiling point 97 to 160 °C (207 to 320 °F; 370 to 433 K)
insoluble
Hazards
Main hazards Explosive
Explosive data
Shock sensitivity High / moderate when wet
Friction sensitivity High / moderate when wet
Detonation velocity 5300 m/s
17,384 ft/s
3.29 miles per second
RE factor 0.83
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YesYN ?)
Infobox references

Acetone peroxide is an organic peroxide and a primary high explosive. It is produced by the oxidation of acetone to yield a mixture of linear monomer and cyclic dimer, trimer, and tetramer forms. The trimer is known as triacetone triperoxide (TATP) or tri-cyclic acetone peroxide (TCAP). Acetone peroxide takes the form of a white crystalline powder with a distinctive bleach-like odor and can explode if subjected to heat, friction, or shock. As a non-nitrogenous explosive, TATP has historically been more difficult to detect, and it has been implicated as the explosive used in terrorist attacks in Europe (2016 Brussels bombings) in 2016 and earlier.

History

Acetone peroxide (specifically, triacetone triperoxide) was discovered in 1895 by Richard Wolffenstein.[1] He was the first researcher to receive a patent for using the peroxide as an explosive compound.

In 1900 Bayer and Villiger described the first synthesis of the dimer and described use of acids for the synthesis of both peroxides.[2] Work on this methodology, and on the various products obtained, was further investigated in the mid-20th century by Milas and Golubović.[3]

Chemistry

The chemical name acetone peroxide is most commonly used to refer to the cyclic trimer triacetone triperoxide (TATP; synonyms, tri-cyclic acetone peroxide, TCAP; peroxyacetone), obtained by a reaction between hydrogen peroxide and acetone in an acid-catalyzed nucleophilic addition, although various further monomeric and dimeric forms are possible.

Synthesis of tri-cyclic acetone peroxide.

Specifically, two dimers, one cyclic (C6H12O4) and one open chain (C6H14O4), as well as an open chain monomer (C3H8O4),[4] can also be formed; under a particular set of conditions of reagent and acid catalyst concentration, the cyclic trimer is the primary product.[3] A tetrameric form has also been described, under different catalytic conditions.[5] Under neutral conditions, the reaction is reported to produce the monomeric organic peroxide.[3] Due to significant angle strain of the chemical bonds in the dimer and monomer, they are even more unstable than the trimer.

Tetrameric acetone peroxide

Organic peroxides in general are sensitive, dangerous explosives, and all forms of acetone peroxide are sensitive to initiation. TATP decomposes explosively; examination of the explosive decomposition of TATP predicts "formation of acetone and ozone as the main decomposition products and not the intuitively expected oxidation products."[6] Very little heat is created by the explosive decomposition of TATP; the foregoing computational analysis suggests that TATP decomposition as an entropic explosion.[6] However, this hypothesis has been challenged as not conforming to actual measurements.[7] The tetrameric form of acetone peroxide, prepared under neutral conditions using a tin catalyst (with a chelator or general inhibitor of radical chemistry present), is reported to be more chemically stable, although still a very dangerous primary explosive.[5]

Some forms of acetone peroxide are prone to loss by sublimation and evaporation.

Several methods can be used for trace analysis of TATP,[8] including gas chromatography/mass spectrometry (GC/MS)[9][10][11][12][13] high performance liquid chromatography/mass spectrometry (HPLC/MS),[14][15][16][17][18] and HPLC with post-column derivitization.[19]

Industrial uses

Ketone peroxides, including acetone peroxide and methyl ethyl ketone peroxide, find application, alongside other compounds such as benzoyl peroxide, as initiators for polymerization reactions—e.g. silicone or polyester resins, in the making of fiberglass-reinforced composites. For these uses, the peroxides are typically in the form of a dilute solution in an organic solvent; methyl ethyl ketone is more common for this purpose, as it is stable in storage.

Acetone peroxides are common and unwanted by-products of oxidation reactions, such as those used in phenol syntheses.

Acetone peroxide and benzoyl peroxide are used as flour bleaching agents to bleach and "mature" flour.[20]

Due to their explosive nature, their presence in chemical processes creates potential hazardous situations. Numerous methods are used to reduce their appearance as byproducts—for instance, shifting pH to more alkaline, adjusting reaction temperature, or adding inhibitors of their production.[21]

Use in improvised explosive devices

TATP and the other explosive forms of acetone peroxide belong to the few high explosives that do not contain nitrogen,[22] and so can pass undetected through scanners designed to detect nitrogenous explosives.[23] Because of its high susceptibility to accidental detonation (and resulting "workplace accidents" in bomb-making shops), TATP has been referred to as the "Mother of Satan."[22] It is used by terrorists for its ability to evade detection aimed at nitrogenous explosives, and due to its low cost and the ease with which its precursors can be obtained.[22] It has been described in popular media as easily prepared from readily available retail ingredients, such as hair bleach and nail polish remover.[24]

As such, TATP has been used in bomb and suicide attacks and in improvised explosive devices, including the London bombings on 7 July 2005, where four suicide bombers killed 52 people and injured more than 700.[25][26] It was one of the explosives used by the "shoe bomber" Richard Reid[26] and was used by the suicide bombers in the November 2015 Paris attacks[24] and 2016 Brussels bombings.[27]

References

  1. ↑
  2. ↑ Baeyer A, Villiger V (1900). "Über die Einwirkung des Caro'schen Reagens auf Ketone" [On the effect of Caro's reagent on ketones]. Berichte der deutschen chemischen Gesellschaft 33 (1): 858–864. doi:10.1002/cber.190003301153.; See also Baeyer A, Villiger V (1900). "Über die Nomenclatur der Superoxyde und die Superoxyde der Aldehyde" [On the nomenclature of peroxides and the peroxide of aldehyde]. Berichte der deutschen chemischen Gesellschaft 33 (2): 2479–2487. doi:10.1002/cber.190003302185.
  3. 1 2 3 Milas NA, Golubović A (1959). "Studies in Organic Peroxides. XXVI. Organic Peroxides Derived from Acetone and Hydrogen Peroxide". Journal of the American Chemical Society 81 (24): 6461–6462. doi:10.1021/ja01533a033.
  4. ↑ This is not the DMDO monomer referred to in the Chembox, but rather the open chain, dihydro monomer described by Milas & Goluboviç, op. cit.
  5. 1 2 Jiang H, Chu G, Gong H, Qiao Q (1999). "Tin Chloride Catalysed Oxidation of Acetone with Hydrogen Peroxide to Tetrameric Acetone Peroxide". Journal of Chemical Research 28 (4): 288–289. doi:10.1039/a809955c.
  6. 1 2 Dubnikova F, Kosloff R, Almog J, Zeiri Y, Boese R, Itzhaky H, Alt A, Keinan E (Feb 2005). "Decomposition of triacetone triperoxide is an entropic explosion" (PDF). Journal of the American Chemical Society 127 (4): 1146–59. doi:10.1021/ja0464903. PMID 15669854.
  7. ↑ Sinditskii VP, Koltsov VI, Egorshev, VY, Patrikeev DI, Dorofeeva OV (2014). "Thermochemistry of cyclic acetone peroxides". Thermochimica Acta 585: 10–15. doi:10.1016/j.tca.2014.03.046.
  8. ↑ Schulte-Ladbeck R, Vogel M, Karst U (Oct 2006). "Recent methods for the determination of peroxide-based explosives". Analytical and Bioanalytical Chemistry 386 (3): 559–65. doi:10.1007/s00216-006-0579-y. PMID 16862379.
  9. ↑ Muller D, Levy A, Shelef R, Abramovich-Bar S, Sonenfeld D, Tamiri T (Sep 2004). "Improved method for the detection of TATP after explosion". Journal of Forensic Sciences 49 (5): 935–8. PMID 15461093.
  10. ↑ Stambouli A, El Bouri A, Bouayoun T, Bellimam MA (Dec 2004). "Headspace-GC/MS detection of TATP traces in post-explosion debris". Forensic Science International. 146 Suppl: S191–4. doi:10.1016/j.forsciint.2004.09.060. PMID 15639574.
  11. ↑ Oxley JC, Smith JL, Shinde K, Moran J (2005). "Determination of the Vapor Density of Triacetone Triperoxide (TATP) Using a Gas Chromatography Headspace Technique". Propellants, Explosives, Pyrotechnics 30 (2): 127. doi:10.1002/prep.200400094.
  12. ↑ Sigman ME, Clark CD, Fidler R, Geiger CL, Clausen CA (2006). "Analysis of triacetone triperoxide by gas chromatography/mass spectrometry and gas chromatography/tandem mass spectrometry by electron and chemical ionization". Rapid Communications in Mass Spectrometry 20 (19): 2851–7. doi:10.1002/rcm.2678. PMID 16941533.
  13. ↑ Romolo FS, Cassioli L, Grossi S, Cinelli G, Russo MV (Jan 2013). "Surface-sampling and analysis of TATP by swabbing and gas chromatography/mass spectrometry". Forensic Science International 224 (1-3): 96–100. doi:10.1016/j.forsciint.2012.11.005. PMID 23219697.
  14. ↑ Widmer L, Watson S, Schlatter K, Crowson A (Dec 2002). "Development of an LC/MS method for the trace analysis of triacetone triperoxide (TATP)". The Analyst 127 (12): 1627–32. doi:10.1039/B208350G. PMID 12537371.
  15. ↑ Xu X, van de Craats AM, Kok EM, de Bruyn PC (Nov 2004). "Trace analysis of peroxide explosives by high performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (HPLC-APCI-MS/MS) for forensic applications". Journal of Forensic Sciences 49 (6): 1230–6. PMID 15568694.
  16. ↑ Cotte-Rodríguez I, Hernandez-Soto H, Chen H, Cooks RG (Mar 2008). "In situ trace detection of peroxide explosives by desorption electrospray ionization and desorption atmospheric pressure chemical ionization". Analytical Chemistry 80 (5): 1512–9. doi:10.1021/ac7020085. PMID 18247583.
  17. ↑ Sigman ME, Clark CD, Caiano T, Mullen R (2008). "Analysis of triacetone triperoxide (TATP) and TATP synthetic intermediates by electrospray ionization mass spectrometry". Rapid Communications in Mass Spectrometry 22 (2): 84–90. doi:10.1002/rcm.3335. PMID 18058960.
  18. ↑ Sigman ME, Clark CD, Painter K, Milton C, Simatos E, Frisch JL, McCormick M, Bitter JL (Feb 2009). "Analysis of oligomeric peroxides in synthetic triacetone triperoxide samples by tandem mass spectrometry". Rapid Communications in Mass Spectrometry 23 (3): 349–56. doi:10.1002/rcm.3879. PMID 19125413.
  19. ↑ Schulte-Ladbeck R, Kolla P, Karst U (Feb 2003). "Trace analysis of peroxide-based explosives". Analytical Chemistry 75 (4): 731–5. doi:10.1021/ac020392n. PMID 12622359.
  20. ↑ Ferrari CG, Higashiuchi K, Podliska JA (1963). "Flour Maturing and Bleaching with Acyclic Acetone Peroxides" (PDF). Cereal Chemistry 40: 89–100.
  21. ↑ Costantini, Michel (1991-03-26) Destruction of acetone peroxide. United States Patent 5003109. Freepatentsonline.com. Retrieved on 2013-02-03.
  22. 1 2 3 Glas K (2006-11-06). "TATP: Countering the Mother of Satan". The Future of Things. Retrieved 24 September 2009. The tremendous devastative force of TATP, together with the relative ease of making it, as well as the difficulty in detecting it, made TATP one of the weapons of choice for terrorists
  23. ↑ "Feds are all wet on airport security". Star-Ledger (Newark, New Jersey). 2006-08-24. Retrieved 11 September 2009. At the moment, Watts said, the screening devices are set to detect nitrogen-based explosives, a category that doesn't include TATP
  24. 1 2 Callimachi R, Rubin AJ, Fourquet L (2016-03-19). "A View of ISIS’s Evolution in New Details of Paris Attacks". The New York Times.
  25. ↑ Naughton P (2005-07-15). "TATP is suicide bombers' weapon of choice". The Times (UK). Archived from the original on 10 February 2008.
  26. 1 2 Vince G (15 July 2005). "Explosives linked to London bombings identified". New Scientist.
  27. ↑ ""La mère de Satan" ou TATP, l'explosif préféré de l'EI" ["Mother of Satan " or TATP , the preferred explosive of IE]. LeVif.be Express (in French).

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