ChemComm
Page 4 of 4
DOI: 10.1039/C4CC09775K
Kudin,J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V.
Barone, B. Mennucci, M. Cossi,G. Scalmani, N. Rega, G. A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R.Fukuda, J.
Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai,
M. Klene,X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken,
C. Adamo, J. Jaramillo, R.Gomperts, R. E. Stratmann, O. Yazyev, A.
J. Austin, R. Cammi, C. Pomelli, J. W.Ochterski, P. Y. Ayala, K.
Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G.
Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D.
K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V.
Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B.
Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.
L.Martin, D. J. Fox, T. Keith, M. A. AlꢀLaham, C. Y. Peng, A.
Nanayakkara, M.Challacombe, P. M. W. Gill, B. Johnson, W. Chen,
M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03 (Revision
D.01), Gaussian, Inc., Wallingford CT, 2004.
The mixture was filtered and the residue washed with cold water
to leave a white solid (yield, 2.3 g, 74%).
Tmelt = 81.0 °C; Tdec (onset) = 363.0 C; IR (KBr) ν 2924, 1554,
1531, 1491, 1454, 1413, 1355, 1325, 1229, 1124, 1080, 1020,
879, 808, 760, 732, 623 cmꢀ1 ; 1H NMR δ 4.0 (CH3) ; 13C NMR δ
147.9, 130.5, 96.7; elemental analysis: (%) calculated for C4H3 I
N4O4 (298.00): C, 16.12; H, 1.01; N, 18.80; found C, 16.15; H,
0.91; N, 18.54.
o
65
70
75
5
10 Conclusions
Polyiodopyrazoles, 3, 4, 5ꢀtriiodopyrazole (1), 1ꢀmethylꢀ3, 4, 5ꢀ
triiodopyrazole (2) and Nꢀdiiodomethylꢀ3, 4, 5ꢀtriiodopyrazole
(3), were synthesized in efficient electrophilic reactions using
molecular iodine in the presence of trifluoroacetic and sulphuric
15 acid; the calculated detonation properties and products suggest
that the compounds may be effective bio agent defeat agents. A
synthetic method was developed as an effective strategy for
introducing an Nꢀdiiodomethyl group into pyrazole. Nitration of
1 and 2 with 100% HNO3 resulted in the formation of the
20 heretofore inaccessible iodo dinitropyrazoles, 4 and 5. These
polyiodopyrazoles may have application not only as ADWs but
also in other areas such as medicinal chemistry, materials science,
and synthetic organic chemistry.
[9] A. Strȍmberg, O. Gropen, U. Wahlgren, J. Comput. Chem. 1983, 4,
181– 186.
80 [10] (a) Q. Zhang, J. Zhang, D. A. Parrish, J. M. Shreeve, Chem. Eur.
J. 2013, 19, 11000ꢀ11006. (b) G. Hervé, C. Roussel, H. Graindorge,
Angew. Chem. 2010, 122, 3245ꢀ3249; Angew. Chem. Int. Ed. 2010,
49, 3177ꢀ3181.
85 [12] A. N. Boa, J. D. Crane, R. M. Kowa, N. H. Sultana, Eur. J. Inorg.
Chem. 2005, 872–878.
The authors gratefully acknowledge Dr. J. P. Hooper, Naval
25 Postgraduate School, Monterey, CA 93943 for Cheetah 6.0
calculations. This work was supported by the Defence Threat
Reduction Agency (HDTRA1–11–1–0034) and the ONR
(NOOO14ꢀ12ꢀ1ꢀ0536).
Notes and references
30 a Department of Chemistry, University of Idaho, Moscow, ID 83844-2343
USA.
E-mail: jshreeve@uidaho.edu
Fax:+1 208-885-9146
‡ Crystal data for 5: C2H7N5O4, FW = 298.00, Crystal dimensions 0.17 ×
35 0.10 × 0.07 mm, Monoclinic, space group P21, a = 6.082(9) Å, b =
8.835(14) Å, c = 8.067(13) Å,
β
= 107.606(19)°, V = 413.2(11) Å3, Z = 2,
Dc = 2.395 mg/m3,
λ
= 0.71073 Å,
ꢀ
= 3.866 mmꢀ1, F(000) = 280, R1 =
0.0229 for 1073 observed (I > 2σI) reflections and 0.0252 for all 1073
reflections, Goodnessꢀofꢀfit = 0.970, 119 parameters. Further details are
40 provided in the ESI†. CCDC 1031880.
[1] J. J. Baker, C. Gotzmer, R. Gill, S. L. Kim, M. Blachek, US Patent
2009 7,568.432.
[2] D. Fischer, T. M. Klapȍtke, J. Stierstorfer, Z. Anorg. Allg. Chem.
45
50
55
2011, 637, 660– 665
[3] (a) C. He, J. Zhang, J. M. Shreeve, Chem. Eur. J. 2013, 19, 7503ꢀ
7509; (b) C. He, D. A. Parrish, J. M. Shreeve, Chem. Eur. J. 2014,
20, 6699 – 6706
[4] (a) R. Hüttel, O. Schäfer, P. Jochum, Liebigs Ann. Chem. 1955, 593,
200–207. (b) J. F. Hansen, Y. I. Kim, L. J. Griswold, G. W. Hoelle,
D. L. Taylor, D. E. Vietti, J. Org. Chem. 1980, 45, 76–80. (c) W.
Holzer, H. Gruber, J. Heterocycl. Chem. 1995, 32, 1351–1354.
[5] (a) D. Giles, E. W. Parnell, J. D. Renwick, J. Chem. Soc. C 1966,
1179ꢀ1184. (b) M. M. Kim, R. T. Ruck, D. Zhao; M. A. Huffman,
Tetrahedron Lett. 2008, 4026ꢀ4028.
[6] E. V. Tretyakov, S. F. Vasilevsky, Mendeleev Commun. 1995, 233–
234.
[7] (a) M. A. Rahman, F. Shito, T. Kitamura, Synthesis 2010, 27ꢀ29. (b)
S. Rozen, D. Zamir, J. Org. Chem. 1990, 55, 3552ꢀ3555.
60 [8] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E.Scuseria, M. A.
Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N.
4
|
Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]