Journal of the American Chemical Society
Page 8 of 10
-
1
1
353, 1326, 1242, 1142, 1075, 1003, 805, 763, 668, 599 cm .
(222.16): Calcd: C 16.22, H 4.54, N 50.44 %.
Found: C 16.38, H 4.47, N 50.81 %.
Overcrowded Chromic Alkene via Encapsulation. J. Am. Chem. Soc.
2012, 134 (42), 17420-17423.
. Bellamy, A. J. FOX-7 (1, 1-Diamino-2, 2-dinitroethene). In High
Energy Density Materials, 2007, 1-33. Springer, Berlin, Heidelberg.
. (a) Zhang, J.; Dharavath, S.; Mitchell, L. A.; Parrish, D. A.;
Shreeve, J. M., Energetic Salts Based on 3,5-Bis(dinitromethyl)-1,2,4-
triazole Monoanion and Dianion: Controllable Preparation,
Characterization, and High Performance. J. Am. Chem. Soc. 2016, 138
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
3 10 8 4
C H N O
2
o
1
8
: White solid. Td (onset): 275 C. H NMR (d
6
-DMSO): 8.54 (br),
-DMSO): δ 159.0, 155.0, 104.2
ppm. IR (KBr): = 3313, 1615, 1541, 1390, 1337, 1293, 1138,
096, 1065, 1001, 961, 763, 620 cm . C H N O (203.16):
3 9 9 2
Calcd: C 17.74, H 4.47, N 62.05 %. Found: C 17.61, H 4.55, N
61.33 %.
3
1
3
6.37 (br) ppm. C NMR (d
6
-1
1
(24), 7500-7503; (b) Vo, T. T.; Parrish, D. A.; Shreeve, J. M., 1,1-
Diamino-2,2-dintroethene (FOX-7) in Copper and Nickel Diamine
Complexes and Copper FOX-7. Inorg. Chem. 2012, 51 (3), 1963-1968;
(c) Vo, T. T.; Zhang, J.; Parrish, D. A.; Twamley, B.; Shreeve, J. M.,
New Roles for 1,1-Diamino-2,2-dinitroethene (FOX-7): Halogenated
FOX-7 and Azo-bis(diahaloFOX) as Energetic Materials and
Oxidizers. J. Am. Chem. Soc. 2013, 135 (32), 11787-11790;
o
o
1
9
: White solid. T
DMSO): 8.35 (br), 7.47 (br) ppm. C NMR (d
58.8, 154.6, 103.9 ppm. IR (KBr): = 3431, 3264, 1689, 1658,
1605, 1544, 1459, 1384, 1279, 1117, 1055, 1001, 784, 753, 725,
m d 6
: 242 C, T (onset): 289 C. H NMR (d -
1
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
6
-DMSO): δ
1
4
. (a) Axthammer, Q. J.; Krumm, B.; Klapötke, T. M., The Exciting
-1
694, 604, 508 cm . C
3
H
8
N
8
O
2
(188.15): Calcd: C 19.15, H 4.29,
Chemistry of 1,1-Diamino-2,2-dinitroethene and 1-Amino-1-
N 59.56 %. Found: C 18.97, H 4.34, N 58.60 %.
hydrazino-2,2-dinitroethene. J. Phys. Chem. A 2017, 121 (18), 3567-
3
579; (b) Li, C.; Feng, Z.; Wang, H.; Zhou, T.; Li, Y.; Xu, K., Aromatic
Synthesis of 10
Nucleophilic Substitution of FOX-7: Synthesis and Properties of 1-
Amino-1-Picrylamino-2,2-Dinitroethylene (APDE) and Its Potassium
Salt [K(APDE)]. ChemPlusChem 2019, 84 (7), 794-801.
5. (a) Evers, J.; Klapötke, T. M.; Mayer, P.; Oehlinger, G.; Welch,
J., α- and β-FOX-7, Polymorphs of a High Energy Density Material,
Studied by X-ray Single Crystal and Powder Investigations in the
Temperature Range from 200 to 423 K. Inorg. Chem. 2006, 45 (13),
Compound 3 (0.43 g, 2.5 mmol) was added slowly to 100%
o
nitric acid (3 mL) at -5 0 C. The reaction mixture was stirred
o
at 0 C for 1 h. The solution was concentrated by air to give a
white solid, which was washed with acetone (5 mL) and dried
in air to give 10.
o
1
6
10: White solid. Td (onset): 120 C. H NMR (d -DMSO): 10.28
4
996-5007. (b) Crawford, M.-J.; Evers, J.; Göbel, M.; Klapötke, T. M.;
1
3
15
(br) ppm. C NMR (d
6
-DMSO): δ 156.0, 151.3, 113.0 ppm. N
Mayer, P.; Oehlinger, G.; Welch, J. M., γ-FOX-7: Structure of a High
Energy Density Material Immediately Prior to Decomposition.
Propellants Explos. Pyrotech. 2007, 32 (6), 478-495.
NMR (d -DMSO): δ 18.3, -21.2, -53.7, -261.1 ppm. IR (KBr):
6
= 3254, 3123, 2987, 2809, 1717, 1617, 1577, 1490, 1433,
1392, 1337, 1308, 1183, 1161, 1146, 1111, 1025, 988, 864, 830,
6
. Gao, H.; Joo, Y.-H.; Parrish, D. A.; Vo, T.; Shreeve, J. M., 1-
Amino-1-hydrazino-2,2-dinitroethene and Corresponding Salts:
Synthesis, Characterization, and Thermolysis Studies. Chem. Euro. J.
2011, 17 (16), 4613-4618.
-1
3 4 8 4
735, 716, 684 cm . C H N O (216.12): Calcd: C 16.67, H 1.87,
N 51.85 %. Found: C 16.89, H 2.08, N 51.79 %.
7
. Frumkin, A. E.; Yudin, N. V.; Suponitsky, K. Y.; Sheremetev, A.
B., 1-Amino-1-hydroxyamino-2,2-dinitroethene: Novel Insights in
Chemistry of FOX-7. Mendeleev Commun. 2018, 28 (2), 135-137.
ASSOCIATED CONTENT
Supporting Information. Crystal structure analysis of compounds
8
. (a) Piercey, D. G.; Chavez, D. E.; Scott, B. L.; Imler, G. H.;
Parrish, D. A., An Energetic Triazolo-1,2,4-Triazine and its N-Oxide.
Angew. Chem. Int. Ed. 2016, 55 (49), 15315-15318; (b) Tang, Y.;
Kumar, D.; Shreeve, J. M., Balancing Excellent Performance and High
Thermal Stability in a Dinitropyrazole Fused 1,2,3,4-Tetrazine. J. Am.
Chem. Soc. 2017, 139 (39), 13684-13687; (c) Pagoria, P., A
Comparison of the Structure, Synthesis, and Properties of Insensitive
Energetic Compounds. Propellants, Explos. Pyrotech.2016, 41 (3),
3
, 4, 5, 9, 10 and 12 and covalent bonding interactions are given in
the Supporting Information. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
4
52-469; (d) Wang, Y.; Liu, Y.; Song, S.; Yang, Z.; Qi, X.; Wang, K.;
Liu, Y.; Zhang, Q.; Tian, Y., Accelerating the Discovery of Insensitive
High-energy-density materials by a Materials Genome Approach. Nat.
Commun. 2018, 9 (1), 2444.
9. Yin, P.; Parrish, D. A.; Shreeve, J. M., Energetic
Multifunctionalized Nitraminopyrazoles and Their Ionic Derivatives:
Ternary Hydrogen-bond Induced High Energy Density Materials. J.
Am. Chem. Soc. 2015, 137 (14), 4778-86.
*
ACKNOWLEDGMENTS
Financial support of the Office of Naval Research (N00014-16-1-
2089), and the Defense Threat Reduction Agency (HDTRA 1-15-
1
0. (a) Temple, C.; Kussner, C. L.; Montgomery, J. A., Reaction of
Some 4-chloro-5-nitropyrimidines with Sodium Azide.
Oxadiazolo[3,4-d]pyrimidine 1-oxides. J. Org. Chem. 1968, 33 (5),
086-2089; (b) Makarov, V. A.; Sedov, A. L.; Nemeryuk, M. P.;
1
-0028) is gratefully acknowledged. This work was supported by
the National Natural Science Foundation of China (No. 21905135),
Province the Natural Science Foundation of Jiangsu Province
2
(BK20190458) and the Fundamental Research Funds for the
Solov'ev, N. P.; Safonova, T. S., Highly Polarized Enamines 1.
Synthesis and Some Properties of β-Tetrazolylenamines. Chem.
Heterocycl. Comd. 1994, 30 (7), 846-850.
11. (a) Biffin, M.; Brown, D.; Lee, T., Pyrimidine Reactions. XV.
Syntheses Involving Oxidation of Hydrazinopyrimidines. Aust. J.
Chem. 1967, 20 (5), 1041-1047; (b) Temple, C.; McKee, R. L.;
Montgomery, J. A., Studies on the Azidoazomethine-Tetrazole
Equilibrium. II. 4-Azidopyrimidines1. J. Org. Chem. 1965, 30 (3), 829-
834.
Central Universities (No.30919011270).
Notes
The authors declare no competing financial interest.
REFERENCES
1
. (a) Yanai, H.; Suzuki, T.; Kleemiss, F.; Fukaya, H.; Dobashi, Y.;
1
2. Carbon, J. A., Heterocyclic Compounds Containing Adjacent
Malaspina, L. A.; Grabowsky, S.; Matsumoto, T., Chemical Bonding
in Polarised Push–Pull Ethylenes. Angew. Chem. 2019, 131 (26), 8931-
Nitro and Guanidino Groups. A Novel Rearrangement of 4-Amino-5-
nitro-6-guanidino-(and 6-ureido)pyrimidine. J. Org. Chem. 1961, 26
8
936; (b) Takezawa, H.; Murase, T.; Fujita, M., Temporary and
(2), 455-461.
Permanent Trapping of the Metastable Twisted Conformer of an
1
3. Bodzioch, A.; Pomikło, D.; Celeda, M.; Pietrzak, A.; Kaszyński,
ACS Paragon Plus Environment