Please do not adjust margins
New Journal of Chemistry
Page 6 of 9
ARTICLE
EA (C5H5N3O4, 171.11 g mol-1): calcd C 35.10, H 2.95, N 24.56% heated to 65
Journal Name
1
2
3
4
5
6
7
8
and found: C 35.27, H 3.06, N 24.48%.
with ethyl acetate. The organic solution waDs OdIr:i1e0d.1o03v9e/rCa9nNhJy0d12r2o7uCs
Na2SO4. The solvent was evaporated, the residue was purified by
silica gel chromatography using benzene as eluent to yield the
desired product 1 (28%).
1-Methyl-2,3,4,5-tetranitropyrrole (1) from (2)
Fuming nitric acid (6 ml) was added dropwise to a solution of 2
(0.4 g, 2.34 mmol) in fuming sulfuric acid. The reaction mixture
was heated at 65 C for 15 min, poured onto ice (100 g),
extracted with ethyl acetate, and dried over anhydrous sodium
sulfate. The solvent was evaporated and the residue was
purified by column chromatography using silica gel and
benzene as eluent to afford the desired compound 1 (35%) as
9
Conflicts of interest
There are no conflicts to declare.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Ackowledgements
1
pale yellow solid; m.p. 100-101° C. H NMR (500 MHz, CD3CN):
δ 4.05 ppm (s, 3H); 13C NMR (125.8 MHz, CD3CN): δ 36.51 ppm.
15N NMR (50.7 MHz, CD3CN): δ -0.92 (N1), 344.77 (N3), 347.44
(N2) ppm. IR: ṽ = 2923, 2853, 1739, 1632, 1561, 1530, 1442,
1380, 1322, 1147, 1043, 900, 818 cm-1. EA (C5H3N5O8, 261.12 g
mol-1): calcd C 23.00, H 1.16, N 26.82% and found: C 23.12, H
1.21, N 26.90%.
Authors thank Defence Research and Development Organization
(DRDO), India for financial support through ACRHEM (Phase II &
Phase III) to University of Hyderabad. Financial and infrastructure
support from the University Grants Commission, New Delhi (through
the UPE and CAS programs), and the Department of Science and
Technology, New Delhi (through the PURSE and FIST programs), are
gratefully acknowledged. V.T. thanks UGC, India and ACRHEM, K. C.
thanks ACRHEM and B.S.K. thanks SERB, India for fellowships.
Authors also thank for Centre for Modelling, Simulation and Design
(CMSD), University of Hyderabad for the computational facility.
1-Methyl-2,3,4,5-tetraiodopyrrole (8)
To a mixture of 1-methylpyrrole (0.457 g, 5.63 mmol) in DMF
(50 mL) was added NIS (8.87 g, 39.4 mmol) portion-wise at 0
C. The reaction mixture was allowed to warm upto room
temperature and stirring was continued for 4 h. The reaction
mixture was poured in saturated Na2CO3 solution, filtered, the
precipitate was washed thoroughly with water and dried. The
pure product 8 was obtained as a white solid (98%). The
characterization data of obtained product matched with the
available literature data.16
References
1
(a) P. Ravi, D. M. Badgujar, G. M. Gore, S. P. Tewari and A. K.
Sikder, Propell. Explos. Pyrotech., 2011, 36, 393; (b) T. M.
Klapötke, A. Penger, C. Pflüger and J. Stierstorfer New. J.
Chem., 2016, 40, 6059; (c) E. C. Johnson, J. J. Sabatini, D. E.
Chavez, R. C. Sausa, E. F. C. Byrd, L. A. Wingard and P. E.
Guzmàn, Org. Process. Res. Dev., 2018, 22, 736; (d) P. W.
Leonard, D. E. Chavez, P. R. Bowden and E. G. Fancois,
Propell. Explos., Pyrotech., 2018, 43, 11; (e) J. C. Bennion, Z.
R. Siddiqi and A. J. Matzger, Chem. Commun., 2017, 53, 6065;
(f) N. Sikder, A. K. Sikder, N. R. Bulakh and B. R. Gandhe, J.
Hazard. Mater., 2004, 113, 35; (g) D. E. Chavez, M. A. Hiskey,
D. L. Naud and D. Parrish, Angew. Chem. Int. Ed., 2008, 47,
8307.
1-Methyl-2,3,4-trinitropyrrole (6)
1-Methyl-2,3,4,5-tetraiodopyrrole (2 g, 3.42 mmol) was added
in small portions to fuming nitric acid (6 mL) at 0 C and the
reaction mixture was heated to 65 C for 30 min. After cooling
to room temperature, the reaction mixture was poured into
crushed ice, neutralized with NaHCO3, filtered, the residue was
washed with cold water to obtain yellow solid. The obtained
mixture (0.608 g) was dissolved in DMF (1 mL) and copper
powder (0.678 g, 10.66 mmol) was added to it. The reaction
mixture was heated to 65 C for 1 h. After cooling to room
temperature, the reaction mixture was filtered through celite
and the filtrate was added to ice water and extracted with
ethyl acetate. The organic layer was washed with water and
dried over anhydrous Na2SO4. The solvent was removed in
vacuo and residue was chromatographed on silica gel by
eluting with hexane-ethyl acetate (7:3) to yield 6 (19%) as pale
yellow solid; m. p. 115 C. 1H NMR (500 MHz, CD3CN): δ 7.93 (s,
1H), 4.40 (s, 3H) ppm; 13C NMR (125.8 MHz, CD3CN): δ 125.27
(C5), (The C2, C3, C4 resonance were not detected), 39.39 (CH3)
ppm. EA (C5H4N4O6, 216.12 g mol-1): calcd C 27.79, H 1.87, N
25.93% and found: C 27.71, H 1.83, N 25.82%.
2
3
(a) D. W. Doll, J. M. Hanks, T. K. Highsmith and G. K. Lund,
WO01/46092A1, 2001; (b) A. Provatas and C. Wall, Propell.
Explos. Pyrotech., 2016, 41, 555.
M. J. Rossi, J. C. Bottaro and D. F. McMillen, Int. J. Chem.
Kinet., 1993, 25, 549; (b) T. B. Brill, P. J. Brush and D. G. Patil,
Combust. Flame., 1993, 99, 178; (c) A. M. Medel, M. C. Lin, K.
Morokuma and C. F. Melius, J. Phys. Chem., 1995, 99, 6842.
A. Hahma, E. Edinsson and H. Östmark, J. Energ. Mater.,
2010, 28, 114.
(a) V. Thottempudi, H. Gao and J. M. Shreeve, J. Am. Chem.
Soc., 2011, 133, 6464; (b) V. Thottempudi and J. M. Shreeve,
J. Am. Chem. Soc., 2011, 133, 19982; (c) Y. Tang, S.
Dharavath, G. H. Imler, D. A. Parrish and J. M. Shreeve, Chem.
-Eur. J., 2017, 23, 9185; (d) H. Xue, H. Gao, B. Twamley and J.
M. Shreeve, Chem. Mater., 2007, 19, 1731; (e) D. Fischer, T.
M. Klapötke, D. G. Piercey and J. Stierstorfer, Chem.–Eur. J.,
2013, 19, 4602; (f) Y. Tang, H. Yang, B. Wu, X. Ju, C. Lu and G.
Cheng, Angew. Chem., Int. Ed., 2013, 52, 4875; (g) W. Liu, S.
Li, Y. Li, Y. Yang, Y. Yu and S. Pang, J. Mater. Chem. A, 2014, 2,
15978; (h) L. A. Wingard, E. C. Johnson, P. E. Guzmán, J. J.
Sabatini, G. W. Drake, E. F. C. Byrd and R. C. Sausa, Eur. J. Org.
Chem., 2017, 1765; (i) J. Zhang, Y. Du, K. Dong, H. Su, S.
Zhang, S. Li and S. Pang, Chem. Mater., 2016, 28, 1472; (j) C.
Li, L. Liang, K. Wang, C. Bian, J. Zhang and Z. Zhou, J. Mater.
4
5
1-Methyl-2,3,4,5-tetranitropyrrole (1) from (6)
Fuming nitric acid (0.7 mL) was added dropwise to a solution of 1-
methyl-2,3,4-trinitropyrrole (0.2 g, 0.92 mmol) in fuming sulfuric
acid (2 mL) at 0 C using ice-salt bath. The reaction mixture was
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins