Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
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This can also be confirmed by regular 2D and decomposed 2D purification.
fingerprint plots. Those O···O close contacts are the dominant 3-trinitromethyl-4-nitro-5-nitramine-1H-pyrazole (5):To a mixture
interaction in compound . The percentage of O···O close of 98% sulfuric acid (6.0 mL) and 100% nitric acid (5.0 mL) was
contacts is above 49.8%. The higher relative frequencies of added 2-(3-amino-1H-pyrazol-5-yl)acetic acid (4) (1.0 g, 7.0 mmol)
close O···O contacts demonstrates more nitro groups exposed at 0 °C. After being stirred for 24 h at room temperature, the
on the molecular surface, which may contribute to its high solution was poured into 30 g of ice and extracted with
DOI: 10.1039/C9NJ02732G
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sensitivities.
dichloromethane (3×15 mL). The organic layer was dried over
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MgSO , and the solvent was evaporated to yield an orange solid 5
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1.21 g (53.1%). H NMR (500 MHz, DMSO-d ): δ 5.23 (br) ppm.
C
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NMR (125 MHz, DMSO-d ): δ 121.11, 123.32, 130.52, 135.24 ppm.
IR (KBr): ṽ 1638.14, 1559.95, 1495.35, 1374.86, 1324.93, 1278.67,
216.60, 1081.92, 1054.55, 1019.32, 955.82, 932.58, 839.26, 789.01,
68.79, 724.92, 689.10, 649.35 cm . Elemental analysis for
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The combination of polynitro groups with heterocycles is an
effective method for the design of high energy density
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oxidizers. A novel oxygen-rich energetic oxidizer, pyrazole
bearing five nitro groups, was synthesized and fully
characterized. The compound exhibits a high density (1.90 g
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C H N O (322.11): calcd C 14.92, H 0.63, N 34.79%. Found: C 14.87,
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2 8 10
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H 0.65, N 34.80%.
cm ), positive heat of formation (0.99 kJ g ), positive oxygen
balance (24.8%) and high specific impulse (262 s). All these
attractive properties highlight its potential application as a
high energy density oxidizer.
Conflicts of interest
There are no conflicts to declare.
Experiment
All reagents were of analytical grade and were used without further
purification. Elemental analyses were performed on a vario EL III
Acknowledgements
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This work was supported by the Science Challenge Project
(TZ2018004) and the National Natural Science Foundation of China
(No. 21676147, 21875110)
CHNOS elemental analyzer. H, C NMR spectra were recorded on
nuclear magnetic resonance spectrometer operating at 500 and 125
MHz, respectively. Chemical shifts in the H and C spectra were
reported in ppm relative to TMS. The DSC spectra were obtained on
a differential scanning calorimeter (Mettler Toledo DSC823e) at a
heating rate of 5 °C min . FT-IR spectra were obtained on a Thermo
Nicolet iS10 spectrometer.
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Reference
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(
v2010.3-0). Data Reduction was performed by using SAINT (v7.68A)
1
and XPREP (v2008/2). Empirical absorption corrections were
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2-(5-amino-1H-pyrazol-3-yl)acetic acid (4):
compound 3 (12.05 g, 82.0 mmol) in a solution of NaOH (10 M, 120
mL) was heated at 95 °C for 12h. Then the mixture was cooled at 8. M. A. Kettner, K. Karaghiosoff, T. M. Klapꢀtke, Muhamed
room temperature and acidified to pH = 3 with concentrated
hydrochloric acid. The precipitate was filtered and added into 280
mL water. The mixture was heated to reflux for 4 h and cooled to
room temperature. The precipitate was filtered. The filtrate was
evaporated under vacuum and the residue was washed ethyl
A suspension of
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acetate. A gray solid (10.50 g) was obtained in a yield of 90.7%. The
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