Paper
Aer the optimization of the reaction conditions (Table 1),
the best result for the synthesis of explosive materials such as
1,1-diamino-2,2-dinitroethene (FOX-7), pentaerythritol tetrani-
trate (PETN), 1,3,5-trinitro-1,3,5-triazinane (RDX) and trinitro-
toluene (TNT) were obtained using [PVI-SO3H]NO3 1.9 g at room
temperature and reuxing CH3CN (Table 2).
RSC Advances
6 J. S. Lee, C. K. Hsu and C. L. Chang, Thermochim. Acta, 2002,
392, 173.
7 Z. A. Alothman, A. H. Bahkali, A. M. Elgorban, M. S. Al-
Otaibi, A. A. Ghfar, S. A. Gabr and A. Y. B. H. Ahmed,
Molecules, 2020, 25, 1393.
8 P. F. Pagoria, G. S. Lee, A. R. Mitchell and R. D. Schmidt,
Thermochim. Acta, 2002, 384, 187.
9 D. M. Badgujar, M. B. Talawar, S. N. Asthana and
P. P. Mahulikar, J. Hazard. Mater., 2008, 151, 289.
Plausible mechanisms for the preparation of explosive
materials were show in Scheme 4 here and Schemes S1–S3 in
the ESI.† At rst, starting materials (pentaerythritol, 1-methyl-4-
nitrobenzene, 2-methylpyrimidine-4,6(1H,5H)-dione, hexa- 10 D. Olender, J. Zwawiak and L. Zaprutko, J. Pharm., 2018, 11,
methylenetetramine) reacts with the in situ generated NO2 54.
radical released from [PVI-SO3H]NO3 to produce intermediate I 11 T. M. Klapotke, C. Petermayer, D. G. Piercey and
and nitrous acid (HNO2). Then, intermediate I reacts with the J. Stierstorfer, J. Am. Chem. Soc., 2012, 134, 20827.
NO2 radical (released from [PVI-SO3H]NO3) to afford interme- 12 K. Zhang, B. Jelier, A. Passera, G. Jeschke and D. Katayev,
diate II. Then, these processes are repeated to obtain the nal
Chem. - Eur. J., 2019, 25, 12929.
products.
13 H. B. Sun, R. Hua and Y. Yin, J. Org. Chem., 2005, 70, 9071.
To compare the performance of [PVI-SO3H]NO3 for the 14 G. S. Prakash, C. Panja, T. Mathew, V. Surampudi,
synthesis of desired nitro materials such as 1,1-diamino-2,2- N. A. Petasis and G. A. Olah, Org. Lett., 2004, 6, 2205.
dinitroethene (FOX-7), pentaerythritol tetranitrate (PETN), 15 L. Lu, H. Liu and R. Hua, Org. Lett., 2018, 20, 3197.
1,3,5-trinitro-1,3,5-triazinane (RDX) and trinitrotoluene (TNT), 16 R. Calvo, K. Zhang, A. Passera and D. Katayev, Nat. Commun.,
we have used various organic and inorganic nitrating reagents.
2019, 10, 1.
´
As Table 3 indicates, [PVI-SO3H]NO3 is the best of choice for the 17 K. Zhang, A. Budinska, A. Passera and D. Katayev, Org. Lett.,
synthesis of explosive materials (Table 3).
2020, 22, 2714.
18 U. Kloeckner and B. J. Nachtsheim, Chem. Commun., 2014,
50, 10485.
Conclusion
19 R. C. Dorey and W. R. Carper, J. Chem. Eng. Data, 1984, 29,
We have prepared poly(vinyl imidazole) sulfonic acid nitrate
93.
[PVI-SO3H]NO3 as a novel polymeric nitrating agent for prepa- 20 M. Kroger and G. Fels, J. Intern. Isot. Soc., 2000, 43, 217.
ration of four energetic materials. [PVI-SO3H]NO3 successfully 21 L. F. Fieser, R. C. Clapp and W. H. Daudt, J. Am. Chem. Soc.,
used for the preparation of FOX-7 (1,1-diamino-2,2-
dinitroethene), pentaerythritol tetranitrate (PETN), 1,3,5- 22 K. Lange, A. Koenig, C. Roegler, A. Seeling and J. Lehmann,
trinitro-1,3,5-triazinane (RDX) and trinitrotoluene (TNT). Also, Bioorg. Med. Chem. Lett., 2009, 19, 3141.
major advantages of the described methodology are high yield 23 B. S. Fedorov and L. T. Eremenko, Russ. Chem. Bull., 1997, 46,
of products without using any co-catalysts, low temperature,
1022.
short reaction times and generality for the preparation of 24 G. M. Blackburn, I. G. Beadham, H. Adams, A. P. Hutchinson
1942, 64, 2052.
energetic materials.
and S. Nicklin, J. Chem. Soc., Perkin Trans. 2, 2000, 2, 225.
25 D. Fischer, T. M. Klapotke and J. Z. Stierstorfer, Z. Anorg. Allg.
Chem., 2011, 637, 660.
26 L. Shi, M. Yu, Y. Zhang, G. Qin, J. Lu and G. Zhao, Chin. J.
Chem., 2011, 29, 283.
Conflicts of interest
There are no conicts to declare.
27 A. A. Astrat'ev, D. V. Dashko, A. Y. Mershin, A. I. Stepanov
and N. A. Urazgil'deev, Russ. J. Org. Chem., 2001, 37, 729.
28 P. Gilinsky-Sharon, H. E. Gottlieb, D. E. Rajsfus,
K. Keinan-Adamsky, V. Marks, P. Aped and A. A. Frimer,
Magn. Reson. Chem., 2012, 50, 672.
Acknowledgements
We thank the Bu-Ali Sina University and Iran National Science
Foundation ((INSF), Grant Number: 98001912) for nancial
support to our research group.
29 J. Zhang, J. Zhang, D. A. Parrish and M. S. Jean'ne, J. Mater.
Chem., 2018, 6, 22705.
30 H. Huang, Y. Shi, Y. Yu and J. Yang, Eur. J. Org. Chem., 2018,
2018, 113.
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© 2021 The Author(s). Published by the Royal Society of Chemistry
RSC Adv., 2021, 11, 8367–8374 | 8373