HNIW, CL-20

• Molecular FormulaC₆H₆N₁₂O₁₂
• Average mass438.185 Da
• 1,3,4,7,8,10-hexanitrooctahydro-1H-5,2,6-(epiminomethanetriylimino)imidazo[4,5-b]pyrazine
  CAS 135285-90-4

• Hexanitrohexaazaisowurtzitane
• 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane
• Octahydro-1,3,4,7,8,10-hexanitro-5,2,6-(iminomethenimino)-1H-imidazo[4,5-b]pyrazine
• HNIW
• 六硝基六氮杂异伍兹烷

ABOUT AUTHOR

Tomasz Gołofit

Thermochemistry, Physical Chemistry, Materials Chemistry

Staff Paweł Maksimowski Wincenty Skupiński Wojciech Pawłowski Waldemar Tomaszewski Tomasz Gołofit Katarzyna Cieślak

Faculty of Chemistry, Division of High Energetic Materials, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland

Hexanitrohexaazaisowurtzitane /ˈhɛksɑːˈnaɪtroʊˈhɛksɑːˌæzɑːˌaɪsoʊˈvʊərtsɪteɪn/, also called HNIW and CL-20, is a nitroamine explosive with the formula C₆H₆N₁₂O₁₂. The structure of CL-20 was first proposed in 1979 by Dalian Institute of Chemical Physics.^[1]In 1980s, CL-20 was developed by the China Lake facility, primarily to be used in propellants. It has a better oxidizer-to-fuel ratio than conventional HMX or RDX. It releases 20% more energy than traditional HMX-based propellants, and is widely superior to conventional high-energy propellants and explosives.

Industrial production of CL-20 was achieved in China in 2011, and it was soon fielded in propellant of solid rockets.^[2] While most development of CL-20 has been fielded by the Thiokol Corporation, the US Navy (through ONR) has also been interested in CL-20 for use in rocket propellants, such as for missiles, as it has lower observability characteristics such as less visible smoke.^[3]

CL-20 has not yet been fielded in any production weapons system, but is undergoing testing for stability, production capabilities, and other weapons characteristics.

Synthesis

THEN CONVERTED TO CL20, HNIW

Synthesis of CL20, HNIW

505	Synthesis of CL-20: By oxidative debenzylation with cerium(IV) ammonium nitrate (CAN)   IPC: Int.Cl.8 C07D		A simple debenzylation approach has been discussed for the synthesis of hexanitrohexaazaisowurtzitane (HNIW or CL-20) one of the most powerful high explosives of today with cerium ammonium (IV) nitrate.
	G M Gore, R Sivabalan*, U R Nair, A Saikia, S Venugopalan & B R Gandhe

First, benzylamine (1) is condensed with glyoxal (2) under acidic and dehydrating conditions to yield the first intermediate compound.(3). Four benzyl groups selectively undergo hydrogenolysis using palladium on carbon and hydrogen. The amino groups are then acetylated during the same step using acetic anhydride as the solvent. (4). Finally, compound 4 is reacted with nitronium tetrafluoroborate and nitrosonium tetrafluoroborate, resulting in HNIW.^[4]

(3R,9R)-2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^3,11.0^5,9]dodecane

• Molecular FormulaC₆H₆N₁₂O₁₂
• Average mass438.185 Da
• (3R,9R)-2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^3,11.0^5,9]dodecan
  (3R,9R)-2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^3,11.0^5,9]dodecane
  (3R,9R)-2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatétracyclo[5.5.0.0^3,11.0^5,9]dodécane
  5,2,6-(Iminomethanetriylimino)-1H-imidazo[4,5-b]pyrazine, octahydro-1,3,4,7,8,10-hexanitro-, (5R,7aR)-

(3R,5S,9R,11S)-2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^3,11.0^5,9]dodecane

• Molecular FormulaC₆H₆N₁₂O₁₂
• Average mass438.185 Da
• (3R,5S,9R,11S)-2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^3,11.0^5,9]dodecan
  (3R,5S,9R,11S)-2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^3,11.0^5,9]dodecane
  (3R,5S,9R,11S)-2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatétracyclo[5.5.0.0^3,11.0^5,9]dodécane
  5,2,6-(Iminomethanetriylimino)-1H-imidazo[4,5-b]pyrazine, octahydro-1,3,4,7,8,10-hexanitro-, (3aR,5S,6R,7aS)

Cocrystal product with HMX

In August 2012, Onas Bolton et al. published results showing that a cocrystal of 2 parts CL-20 and 1 part HMX had similar safety properties to HMX, but with a greater firing power closer to CL-20. ^[5][6]

Cocrystal product with TNT

In August 2011, Adam Matzger and Onas Bolton published results showing that a cocrystal of CL-20 and TNT had

The synthesis of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^5,9.0^3,11]-dodecane (HBIW) is the first stage in the production of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.05,9.03,11] dodecane (CL-20), which is the most potent explosive known today. Because of the high performance characteristics of CL-20, a number of research projects are being conducted worldwide on CL-20 synthesis, properties and applications

Scale-Up Synthesis of Hexabenzylhexaazaisowurtzitane, an Intermediate in CL-20 Synthesis

Tomasz Gołofit^*† , Paweł Maksimowski^† , Piotr Szwarc^‡, Tomasz Cegłowski^‡, and Joanna Jefimczyk^†

^† Faculty of Chemistry, Division of High Energetic Materials, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland

^‡Chemical Works “NITRO−CHEM” S.A., Wojska Polskiego 65 A, 85−825 Bydgoszcz, Poland

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00101

*E-mail: tomgol@ch.pw.edu.pl.

After successful synthesis of hexabenzylhexaazaisowurtzitane (HBIW) on a laboratory scale (0.25 L reactor), it was performed on a multilaboratory scale (10 L reactor) and subsequently in an experimental installation in which a 300 L reactor was built. Seven syntheses were carried out in the unit on a pilot scale to produce 250 kg of HBIW. The pilot-scale syntheses ran with a yield comparable to those observed for the processes conducted on a large-laboratory scale. Some modifications were suggested that allowed for reduction of the HBIW weight unit by approximately 50%

HBIW was 89%. FTIR υ (cm^–1): 3022, 2835, 1954, 1669, 1602, 1492, 1451, 1396, 1351, 1302, 1264, 1208, 1169, 1140, 1122, 1072, 1057, 1028, 1017, 986, 926, 896, 828, 792, 781, 749, 732, 698. ¹H NMR (CDCl₃, 400 MHz): δ 7.39–7.42 (m, 30 H, phenyl CH), 4.33 (s, 4 H, CH2), 4.26–4.27 (d, 8 H, CH2), 4.21 (s, 4 H, CH), 3.75 (s, 2, H, CH).

References

1. Jump up^ 王征, 和霄雯 (2016-04-19). “北理工的爆轰速度 中国力量的可靠基石”. 北京理工大学新闻网.
2. Jump up^ 黎轩平 (2016-04-23). ““我们要在宇宙空间占一个位置！””. 北京理工大学新闻网.
3. Jump up^ Yirka, Bob (9 September 2011). “University chemists devise means to stabilize explosive CL-20”. Physorg.com. Retrieved 8 July 2012.
4. Jump up^ Nair, U. R.; Sivabalan, R.; Gore, G. M.; Geetha, M.; Asthana, S. N.; Singh, H. (2005). “Hexanitrohexaazaisowurtzitane (CL-20) and CL-20-based formulations (review)”. Combust. Explos. Shock Waves. 41 (2): 121–132. doi:10.1007/s10573-005-0014-2.
5. Jump up^ High Power Explosive with Good Sensitivity: A 2:1 Cocrystal of CL-20:HMX, Crystal Growth & Design (American Chemical Society), 2012, 12 (9), pp 4311–4314, DOI: 10.1021/cg3010882, Publication Date (Web): August 7, 2012, accessed 7 September 2012
6. Jump up^ Powerful new explosive could replace today’s state-of-the-art military explosive, SpaceWar.com, 6 September 2012, accessed 7 September 2012
7. Jump up^ Angewandte Chemie International Edition
8. Jump up^ Things I Won’t Work With: Hexanitrohexaazaisowurtzitane

Further reading

• Bolton, Onas; Adam J. Matzger (September 12, 2011). “Improved Stability and Smart-Material Functionality Realized in an Energetic Cocrystal”. Angewandte Chemie. 123 (38): 9122–9125. doi:10.1002/ange.201104164. Retrieved 8 July 2012.
• Lowe, Derek (11 November 2011) “Things I won’t work with: Hexanitrohexaazaisowurtzitane”

////////////////CL 20, 135285-90-4, HNIW

Hexanitrohexaazaisowurtzitane

Names
IUPAC name 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.03,11.05,9]dodecane
Other names CL-20 Hexanitrohexaazaisowurtzitane 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane Octahydro-1,3,4,7,8,10-hexanitro-5,2,6-(iminomethenimino)-1H-imidazo[4,5-b]pyrazine HNIW Octahydro-1,3,4,7,8,10-hexanitro-5,2,6-(iminomethenimino)-1H-imidazo[4,5-b]pyrazine 5,2,6-(Iminomethenimino)-1H-imidazo[4,5-b]pyrazine, octahydro-1,3,4,7,8,10-hexanitro- isowurtzitane, hexanitrohexaaza- Octahydro-1,3,4,7,8,10-hexanitro-5,2,6-(iminomethenimino)-1H-imidazo(4,5-b)pyrazine
Identifiers
CAS Number	135285-90-4
3D model (JSmol)	Interactive image Interactive image
Abbreviations	CL-20, HNIW
ChEBI	CHEBI:77327
ChemSpider	8064994  9223599 (3R,9R)-dodec  9594121 (3R,5S,9R,11S)- dodec
ECHA InfoCard	100.114.169
PubChem CID	9889323 11048432 (3R,9R)-dodec 11419235 (3R,5S,9R,11S)- dodec
InChI[show]
SMILES[show]
Properties
Chemical formula	C 6N 12H 6O 12
Molar mass	438.1850 g mol−1
Density	2.044 g cm−3
Explosive data
Detonation velocity	9.38 km s−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

• 1.Bayat, Y.; Malmir, S.; Hajighasemali, F.; Dehghani, H. Cent. Eur. J. Energy Mater. 2015, 12, 439– 458
• 2.Bayat, Y.; Zarandi, M.; Khadiv-Parsi, P.; Salimi, A. Cent. Eur. J. Energy Mater. 2015, 12, 459– 472
• 3.Gołofit, T.; Zyśk, K. J. J. Therm. Anal. Calorim. 2015, 119, 1931– 1939, DOI: 10.1007/s10973-015-4418-2
• 4.Maksimowski, P.; Adamiak, J. Propellants, Explos., Pyrotech. 2010, 35, 353– 358, DOI: 10.1002/prep.200900057