Optimization Studies on Synthesis of TKX-50
N-Chlorosuccinimide (2 equiv.) at 0 ℃ was added
to the solution of glyoxime in NMP. The reaction mix-
ture was allowed to stir at room temperature for 1 h,
then cooled to 0 ℃ and 2 equiv. of sodium azide were
added and stirred at this temperature for 45 min. To the
resulting solution of diazidoglyoxime in NMP, contain-
ing succinimide, sodium chloride and by-products from
previous stages, dry 1,4-dioxane was added followed by
saturation with gaseous hydrogen chloride at 0 ℃. On
the next day all volatiles were removed under reduced
pressure, the residue was triturated with NaOH, filtered
and converted into TKX-50 with 74% overall yield from
glyoxime (Table 7, Entry 1).
theses diazidoglyoxime cyclization to 1,1'-BTO or its
acyl derivatives was studied and optimized. The possi-
bility of high-yield preparation of 1,1'-BTO and its de-
rivatives (TKX-50 and ABTOX) using both Klapötke
and Tselinskii modified procedures has been shown.
Scope and limitations of 1,1'-BTO derivatives synthesis
(using the example of the TKX-50) and its dependence
on the nature of solvents, catalyst and temperature has
been shown. One-pot five-step synthesis of TKX-50
from glyoxime with 74% yield was described.
References
[1] Badgujar, D. M.; Talawar, M. B.; Asthana, S. N.; Mahulikar, P. P. J.
Hazard. Mater. 2008, 151, 289.
[2] Klapötke, T. M. Chemistry of High-energy Materials, 2. ed., De
Gruyter, Berlin, 2012.
[3] Sikder, A. K.; Sikder, N. J. Hazard. Mater. 2004, 112, 1.
[4] Talawar, M. B.; Sivabalan, R.; Anniyappan, M.; Gore, G. M.;
Asthana, S. N.; Gandhe, B. R. Combust., Explos. Shock Waves (Engl.
Trans.) 2007, 43, 62.
[5] Agrawal, J. P. High Energy Materials: Propellants, Explosives and
Pyrotechnics, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim,
2010.
Table 7 One-pot preparation of TKX-50 from glyoxime
Entry Conditions 1
Conditions 2 Conditions 3 Yield/%
dry 1,4-dioxane,
dry NMP, 2 equiv.
NCS, 1 h, r.t.
1
NaN3, NMP
74
68
56
HCl
dry NMP, 2 equiv.
NCS, 1 h, r.t.
2
NaN3, NMP dry Et2O, HCl
dry DMF, 2 equiv.
NCS, 1 h, r.t.
dry 1,4-dioxane,
3
NaN3, DMF
HCl
[6] Talawar, M. B.; Sivabalan, R.; Mukundan, T.; Muthurajan, H.; Sik-
der, A. K.; Gandhe, B. R.; Rao, A. S. J. Hazard. Mater. 2009, 161,
589.
[7] Brinck, T. Green Energetic Materials, John Wiley & Sons, Chiches-
ter, West Sussex, United Kingdom, 2014.
[8] Fischer, N.; Fischer, D.; Klapötke, T. M.; Piercey, D. G.; Stierstorfer,
J. J. Mater. Chem. 2012, 22, 20418.
[9] Sinditskii, V. P.; Filatov, S. A.; Kolesov, V. I.; Kapranov, K. O.;
Asachenko, A. F.; Nechaev, M. S.; Lunin, V. V.; Shishov, N. I.
Thermochim. Acta 2015, 614, 85.
[10] Zhang, C.; Jin, S.; Chen, S.; Zhang, Y.; Qin, L.; Wei, X.; Shu, Q. J.
Chem. Eng. Data 2016, 61, 1873.
[11] Niu, H.; Chen, S.; Jin, S.; Shu, Q.; Li, L.; Shang, F. J. Energ. Mater.
2016, 34, 416.
[12] Niu, H.; Chen, S.; Jin, S.; Li, L.; Jing, B.; Jiang, Z.; Ji, J.; Shu, Q. J.
Therm. Anal. Calorim. 2016, 126, 473.
[13] Yu, Y.; Chen, S.; Li, X.; Zhu, J.; Liang, H.; Zhang, X.; Shu, Q. RSC
Adv. 2016, 6, 20034.
A similar one-pot reaction with dry ether instead of
1,4-dioxane yielded 68% of TKX-50 (Table 7, Entry 2).
Analogous preparation and isolation procedure of
TKX-50 with dry DMF instead of dry NMP yielded
56% of TKX-50 (Table 7, Entry 3). As it can be seen
from Table 7, the best cosolvents for TKX-50 one-pot
synthesis are: NMP (Table 7, Entry 1 vs. Entry 3) for
glyoxime chlorination and azidation stages and
1,4-dioxane (Table 7, Entry 1 vs. Entry 2) for cycliza-
tion of diazidoglyoxime to 1,1'-BTO. Thus, it is possible
to obtain TKX-50 from glyoxime using optimized
one-pot procedure with 74% yield for 5 steps without
dangerous gaseous chlorine using.
The synthesis procedure for ABTOX follows the
same lines as the synthesis procedure for TKX-50, until
the disodium 5,5'-bistetrazole-1,1'-diolatetetrahydrate is
obtained. In the case of ABTOX it is necessary to add a
somewhat greater excess of ammonium salt, since the
water-solubility of ABTOX is somewhat greater than
that of TKX-50.
[14] Ju, W.; Ling, F.; Gu, Y.; Luo, J. Chin. J. Energ. Mater. 2015, 23, 887.
[15] Li, M.; Zhao, F.; Luo, Y.; Xu, S.; Yao, E. Chin. J. Energ. Mater. 2014,
22, 286.
[16] Zhao, T.; Tian, J.; Li, L.; Fan, G., Zhang, G.; Li, H.; Huang, M. Chin.
J. Energ. Mater. 2014, 22, 744.
[17] Zhu, Z.; Jiang, Z.; Wang, P.; Lu, M.; Shu, Q.; Yu, X. Chin. J. Energ.
Mater. 2014, 22, 332.
[18] Williams, D. B. G.; Lawton, M. J. Org. Chem. 2010, 75, 8351.
[19] Plenkiewicz, J. Tetrahedron Lett. 1975, 5, 341.
[20] Tselinskii, I. V.; Mel'nikova, S. F.; Romanova, T. V. Russ. J. Org.
Chem. 2001, 3, 430.
Conclusions
The most critical step of TKX-50 and ABTOX syn-
(Zhao, C.)
Chin. J. Chem. 2016, XX, 1—5
© 2016 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
5