View source for Chemistry:Hexamethylene triperoxide diamine

{{chembox
| verifiedrevid = 415524053
| Name = 
| ImageFile = 
| ImageFile1 = HMTD structure.png
| ImageSize1 = 150px
| ImageFile2 = Heksametylenotriperoksydiamina.JPG
| ImageSize2 = 
| ImageFile3 = 
| ImageSize3 = 
| PIN = 3,4,8,9,12,13-Hexaoxa-1,6-diazabicyclo[4.4.4]tetradecane
| OtherNames = 
| SystematicName = 
| Section1 = {{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 55052
| InChI = 1/C6H12N2O6/c1-7-2-11-13-5-8(4-10-9-1)6-14-12-3-7/h1-6H2
| InChIKey = HMWPNDNFTFSCEB-UHFFFAOYAC
| ChEMBL_Ref = {{ebicite|correct|EBI}}
| ChEMBL = 346085
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/C6H12N2O6/c1-7-2-11-13-5-8(4-10-9-1)6-14-12-3-7/h1-6H2
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = HMWPNDNFTFSCEB-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|??}}
| CASNo = 283-66-9
| PubChem = 61101
| SMILES = C1N2COOCN(COO1)COOC2
}}
| Section2 = {{Chembox Properties
| Formula = C<sub>6</sub>H<sub>12</sub>N<sub>2</sub>O<sub>6</sub>
| MolarMass = 208.17 g/mol
| Appearance = White crystalline solid
| Density = 1.57 g/cm<sup>3</sup>
| MeltingPt = Decomposes at 75&nbsp;°C<br>Ignites spontaneously at 133&nbsp;°C
| BoilingPt =
| Solubility = }}
| Section3 = {{Chembox Hazards
| GHSPictograms = {{GHS01}} {{GHS07}}
| GHSSignalWord = '''DANGER'''
| HPhrases = {{H-phrases|202|205|241|300|315|318|335}}
| PPhrases = {{P-phrases|102|220|243|250|261|264|280|283|370+380|372|404}}
| NFPA-F = 1
| NFPA-H = 1
| NFPA-R = 4
| MainHazards = Explosive
| FlashPt = 
| AutoignitionPt = }}
| Section4 = 
| Section5 = 
| Section6 = {{Chembox Explosive
| ShockSens = High
| FrictionSens = Very High
| DetonationV = ~2800 [[Metre per second|m/s]] (at around 0.4 g/cm<sup>3</sup>) - 5100 [[Metre per second|m/s]] at around 1.1 g/cm<sup>3</sup> 
| REFactor = 0.74}}
}}

'''Hexamethylene triperoxide diamine''' ('''HMTD''') is a <!-- note to editors: "high explosive", not "highly explosive", is the correct term --> high explosive [[Chemistry:Organic compound|organic compound]]. HMTD is an [[Chemistry:Organic peroxide|organic peroxide]], a [[Chemistry:Heterocyclic compound|heterocyclic compound]] with a cage-like structure. It is a primary explosive. It has been considered as an initiating explosive for blasting caps in the early part of 20th century, mostly because of its high initiating power (higher than that of [[Chemistry:Mercury(II) fulminate|mercury fulminate]]) and its inexpensive production. As such, it was quickly taken up as a primary explosive in mining applications.<ref>Taylor, C. A.; Rinkenbach, W. H. ''Army Ordnance'' '''1924'''. ''5'', 463–466{{Verify source|Is 1924 the volume or the year? What is the title of the article? Is Army Ordnance really the magazine/journal title? Or is it just Ordnance?|date=March 2009}}</ref> However, it has since been superseded by more (chemically) stable compounds such as dextrinated [[Chemistry:Lead(II) azide|lead azide]] and DDNP (which contains no lead or mercury). HMTD is widely used in amateur-made blasting caps.

==Preparation and structure==
First synthesised in 1885 by the German chemist Ludwig Legler,<ref>{{cite journal |last=Legler |first=L. |year=1885 |title=Ueber Producte der langsamen Verbrennung des Aethyläthers |url=http://gallica.bnf.fr/ark:/12148/bpt6k90703s/f1537.chemindefer |journal=Berichte der Deutschen Chemischen Gesellschaft |volume=18 |issue=2 |pages=3343–3351 |doi=10.1002/cber.188501802306}}</ref> HMTD may be prepared by the reaction of an aqueous solution of [[Chemistry:Hydrogen peroxide|hydrogen peroxide]] and hexamine in the presence of an acid [[Chemistry:Catalyst|catalyst]], such as [[Chemistry:Citric acid|citric acid]], acetic acid or dilute [[Chemistry:Sulfuric acid|sulfuric acid]]. The hydrogen peroxide needs to be at least 12% w/w concentration, as lower concentrations lead to poor yields. Citric acid is overall superior to other acids, providing a yield of up to about 50%.

The molecule adopts a cage-like structure with the nitrogen atoms having an unusual trigonal planar geometry.<ref>{{cite journal|last=Schaefer|first=William P.|author2=Fourkas, John T. |author3=Tiemann, Bruce G. |title=Structure of hexamethylene triperoxide diamine|journal=Journal of the American Chemical Society|date=April 1985|volume=107|issue=8|pages=2461–2463|doi=10.1021/ja00294a043}}</ref>

==Properties as an explosive==
Like other organic peroxides, such as [[Chemistry:Acetone peroxide|acetone peroxide]] (TATP), HMTD is unstable and detonates upon shock, friction, static electricity discharges, concentrated sulfuric acid, strong UV radiation and heat. Cases of detonation caused by the simple act of screwing a lid on a jar containing HMTD have been reported.<ref>Stúpajúci trend podomáckej výroby výbušnin a udalosti s tým spojené, Kriminalistický a expertízny ústav Policajného zboru, p. 8 http://www.unms.sk/swift_data/source/dokumenty/skusobnictvo/upravy_2009/odborne_seminare_2008/KEU_BA_01_10_2008.pdf {{Webarchive|url=https://web.archive.org/web/20210923170016/https://www.unms.sk/swift_data/source/dokumenty/skusobnictvo/upravy_2009/odborne_seminare_2008/KEU_BA_01_10_2008.pdf |date=23 September 2021 }}, written in Slovak</ref> Common static electricity discharges have been reported to cause detonation.<ref>Explosive Properties of Primary Explosives - Springer, p.21, section 2.33, {{ISBN|978-3-642-28436-6}}, https://www.springer.com/cda/content/document/cda_downloaddocument/9783642284359-c1.pdf?SGWID=0-0-45-1379807-p174306459</ref> It is, however, less unstable than many other peroxides under normal conditions; exposure to ultraviolet light increases its sensitivity. It also reacts with most common metals, which can lead to [[Physics:Detonation|detonation]]. HMTD is chemically very stable when pure (free of acids, bases, and metal ions) and does not quickly sublime like its acetone counterparts.

HMTD is a more powerful initiating explosive than mercury fulminate, but its poor thermal and chemical stability prevents its use in detonators.<ref name="Organic Chemistry of Explosives">{{cite book
|author1=Hodgson, Robert |author2=Agrawal, Jai P. | title=Organic Chemistry of Explosives
| publisher=Wiley
| year=2007
| pages=414
| isbn=
| oclc=
}}</ref> Nevertheless, HMTD is one of the three most widely used primary explosives in improvised, amateur made blasting caps. The other being TATP and [[Chemistry:Silver acetylide|silver acetylide]].

HMTD is a common source of injury among amateur chemists, particularly finger amputations. Most of these injuries are caused by small amounts of HMTD that inadvertently detonate in close proximity of fingers, since small amounts (grams) are generally not powerful enough to amputate fingers from distances larger than 5 – 10&nbsp;cm.<ref>Stúpajúci trend podomáckej výroby výbušnin a udalosti s tým spojené, Kriminalistický a expertízny ústav Policajného zboru, p. 8 http://www.unms.sk/swift_data/source/dokumenty/skusobnictvo/upravy_2009/odborne_seminare_2008/KEU_BA_01_10_2008.pdf {{Webarchive|url=https://web.archive.org/web/20210923170016/https://www.unms.sk/swift_data/source/dokumenty/skusobnictvo/upravy_2009/odborne_seminare_2008/KEU_BA_01_10_2008.pdf |date=23 September 2021 }}, written in Slovak</ref> Experienced amateurs handle HMTD in such a manner as to avoid any close contact between fingers and the explosive itself, from synthesis to final detonation. Such measures, for example, include using multiple filter papers during the filtration step that are exchanged as not to have more than 0.2 g of HMTD on a single filter paper, pre-bent papers with cotton wrapped wooden rods for manipulation and blast mitigation devices for final filling.

Calculated (Explo5) detonation pressure P<sub>cj</sub> at crystal density 1.597 g/cm<sup>3</sup> is 218 kbar with velocity of detonation VoD = 7777&nbsp;m/s. Explosion temperature is 3141 K, energy of explosion is 5612 kJ/kg (or 3400 - 4000 kJ/kg per various sources) and volume of explosion gases at STP is calculated to be 826 L/kg. Loose powder has density close to 0.4 g/cm<sup>3</sup>, hence the common detonation velocities are closer to 3000&nbsp;m/s and P<sub>cj</sub> is closer to 15 kbar.<ref>{{Cite book | url=https://books.google.com/books?id=hX3mBgAAQBAJ&q=HMTD+detonation+pressure+pressure&pg=PA524 |title = The Chemistry of Peroxides|isbn = 9781118412718|year=2015}}</ref>

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| footer = Detonation velocity of HMTD at given density. Detonation pressure at given density (estimate).
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==Sensitivity==
HMTD is overall slightly more sensitive than fresh TATP and can be considered to be slightly more dangerous than an average primary explosive. The variance of friction force between different surfaces (e.g. different kinds of paper) is often greater than the variance between the friction sensitivity of a given pair of primary explosives. This leads to different values for friction sensitivity measured at different laboratories.

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| footer = Sensitivity of HMTD compared to other primary explosives an PETN.}}

==Terrorism==
Despite no longer being used in any military application, and despite its shock sensitivity, HMTD remains a common home-made explosive and has been used in a large number of suicide bombings and other attacks throughout the world.  For example, it was one of the components in the explosives intended to bomb Los Angeles International Airport in the [[Religion:2000 millennium attack plots|2000 millennium attack plots]]<ref name="febninth">{{cite web|url=http://www.nefafoundation.org/miscellaneous/US_v_Ressam_9thcircuitappeals0210.pdf |title=U.S. v. Ressam |last=U.S. Court of Appeals for the Ninth Circuit |date=2 February 2010 |accessdate=27 February 2010 |url-status=dead |archiveurl=https://web.archive.org/web/20121004023628/http://www.nefafoundation.org/miscellaneous/US_v_Ressam_9thcircuitappeals0210.pdf |archivedate=4 October 2012}}</ref><ref name="comp">{{cite web|url=http://nefafoundation.org/miscellaneous/FeaturedDocs/U.S._v_Ressam_Complaint.pdf|title=Complaint; U.S. v. Ressam|date=December 1999|publisher=NEFA Foundation|accessdate=26 February 2010|url-status=dead|archiveurl=https://web.archive.org/web/20120301162643/http://nefafoundation.org/miscellaneous/FeaturedDocs/U.S._v_Ressam_Complaint.pdf|archivedate=1 March 2012}}</ref>
and the 2016 New York and New Jersey bombings,<ref>{{cite news|date=20 September 2016|title=7 questions we have about bombings in New York and New Jersey|url=http://www.cnn.com/2016/09/20/us/new-york-new-jersey-bomb-questions/|accessdate=20 September 2016|work=CNN|first=Susannah|last=Cullinane|author2=Shimon Prokupecz|author3=Emanuella Grinberg|author4=Holly Yan|author2-link=Shimon Prokupecz}}</ref> as well as one of the components of the explosives attempted to be made by the neo-Nazi terrorist organization [[Organization:Atomwaffen Division|Atomwaffen Division]] in the United States.<ref>{{Cite AV media|url=https://www.pbs.org/wgbh/frontline/film/documenting-hate-new-american-nazis/|title=Documenting Hate: New American Nazis|minutes=15|publisher=PBS/ProPublica|series= ''Frontline''|first=A.C.|last=Thompson|language=en-US|date=2018-11-20|access-date=2019-02-19}}</ref>

==References==
{{reflist|colwidth=30em}}

{{DEFAULTSORT:Hexamethylene Triperoxide Diamine}}
[[Category:Organic peroxides]]
[[Category:Explosive chemicals]]
[[Category:Diamines]]

{{Sourceattribution|Hexamethylene triperoxide diamine}}