Hexanitroethane Explained

Hexanitroethane (HNE) is an organic compound with chemical formula C2N6O12 or (O2N)3C-C(NO2)3. It is a solid matter with a melting point of 135 °C.

Hexanitroethane is used in some pyrotechnic compositions as a nitrogen-rich oxidizer, e.g. in some decoy flare compositions and some propellants. Like hexanitrobenzene, HNE is investigated as a gas source for explosively pumped gas dynamic laser.

A composition of HNE as oxidizer with boron as fuel is being investigated as a new explosive.[1]

Preparation

The first synthesis was described by Wilhelm Will in 1914, using the reaction between the potassium salt of tetranitroethane with nitric acid.[2]

C2(NO2)4K2 + 4 HNO3 → C2(NO2)6 + 2 KNO3 + 2 H2OA practicable method for industrial use starts with furfural,[3] which first undergoes oxidative ring-opening by bromine to mucobromic acid.[4] In the following step, mucobromic acid is reacted with potassium nitrite at just below room temperature to form the dipotassium salt of 2,3,3-trinitropropanal. The final product is obtained by nitration with nitric acid and sulfuric acid at −60 °C.

Properties

The thermal decomposition of hexanitroethane has been detected at 60 °C upwards in both the solid and solution phases.[5] Above 140 °C, this can occur explosively.[6] The decomposition is first order and is significantly faster in solution than in the solid. For the solid, the following reaction can be formulated:[5]

C2(NO2)6 → 3 NO2 + NO + N2O + 2 CO2For the decomposition in solution, tetranitroethylene is first formed and can be trapped and detected as a Diels–Alder adduct, for example with anthracene or cyclopentadiene.[7] [8]

References

  1. http://stinet.dtic.mil/oai/oai?&verb=getRecord&metadataPrefix=html&identifier=ADA064096 Compatibility Testing of Hexanitroethane with Boron
  2. Will. W.. 1914. Über das Hexanitro-äthan. Berichte der Deutschen Chemischen Gesellschaft. de. 47. 1. 961–965. 10.1002/cber.191404701154.
  3. US. 3101379. Synthesis of hexanitroethane. 1961-01-04.
  4. Taylor. G.. 2015. MUCOBROMIC ACID. Organic Syntheses. 11–12. 10.15227/orgsyn.000.0011.
  5. Marshall. Henry P.. Borgardt. Frank G.. Noble. Paul. 1965. Thermal Decomposition of Hexanitroethane 1a,b. The Journal of Physical Chemistry. en. 69. 1. 25–29. 10.1021/j100885a007. 0022-3654.
  6. Book: Bretherick, L.. Bretherick's Handbook of Reactive Chemical hazards. Urben, P. G.. 18 March 2017. 978-0-08-101059-4. 8th. Amsterdam. 240–241. 982005430.
  7. Griffin. T. Scott. Baum. Kurt. 1980. Tetranitroethylene. In situ formation and Diels-Alder reactions. The Journal of Organic Chemistry. en. 45. 14. 2880–2883. 10.1021/jo01302a024. 0022-3263.
  8. Tzeng. Dongjaw. Baum. Kurt. 1983. Reactions of hexanitroethane with alcohols. The Journal of Organic Chemistry. en. 48. 26. 5384–5385. 10.1021/jo00174a053. 0022-3263.

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