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Y. Ling et al.
PAPER
1H NMR (500 MHz, CDCl3): δ = 4.08–4.02 (m, 2 H), 3.96–3.89 (m,
4 H), 3.85–3.79 (m, 2 H), 3.29 (s, 2 H), 2.38 (d, J = 10 Hz, 2 H),
2.23–2.18 (m, 2 H), 1.99 (s, 2 H), 1.74 (s, 2 H).
13C NMR (125 MHz, CDCl3): δ = 121.6, 108.9, 64.8, 64.4, 40.3,
34.7, 30.9, 27.9.
white solid (0.21 g). Finally, 1 was obtained as a white solid; com-
bined yield: 0.81 g (47%).
Mp 198.9–200.4 °C.
FTIR: 3010, 1580, 1474, 1358, 935, 839 cm–1.
1H NMR (500 MHz, CDCl3): δ = 4.82–4.77 (m, 2 H), 3.40–3.10 (m,
4 H), 2.76–2.68 (m, 2 H), 2.07–2.03 (m, 2 H).
13C NMR (125 MHz, CDCl3): δ = 119.7, 119.4, 37.5, 32.7, 30.3,
29.8.
Anal. Calcd for C14H18N2O8: C, 49.12; H, 5.30; N, 8.18. Found: C,
49.23; H, 5.18; N, 8.34.
4,4-Dinitroadamantane-2,6-dione (14)9a
A mixture of 13 (2.5 g, 7.3 mmol), concd H2SO4 (45 mL) and CH2-
Cl2 (200 mL) was stirred at r.t. for 3 h. Then, the reaction mixture
was poured into an ice–water mixture (300 mL). The organic layer
was washed with sat. NaHCO3 solution (50 mL) and brine (50 mL),
dried over Na2SO4 and filtered. The solvent was removed under re-
duced pressure to give 14 as a white solid; yield: 1.76 g (95%).
Anal. Calcd for C10H10N6O12: C, 29.57; H, 2.48; N, 20.69. Found:
C, 29.43; H, 2.56; N, 20.48.
Acknowledgment
We are grateful to Jinjian Liu for help and advice concerning the
cultivation of the single crystal of HNA and to Huaqin Wang for the
single crystal structure analysis.
Mp 246.5–247.8 °C.
FTIR: 2932, 1738, 1558, 1463, 1371, 952, 848 cm–1.
1H NMR (500 MHz, DMSO-d6): δ = 3.84 (s, 2 H), 2.71 (s, 2 H),
2.51–2.35 (m, 4 H), 2.03–1.99 (m, 2 H).
13C NMR (125 MHz, DMSO-d6): δ = 203.7, 123.9, 51.0, 43.3, 41.8,
32.9.
Supporting Information for this article is available online
at
10.1055/s-00000084.SunogIpimrfiantoSuIpg
n
fonirtat
ori
Anal. Calcd for C10H10N2O6: C, 47.25; H, 3.97; N, 11.02. Found: C,
47.36; H, 4.12; N, 10.83.
References
2,6-Bis(hydroxyimino)-4,4-dinitroadamantane (15)9a
(1) (a) Zhang, M. X.; Eaton, P. E.; Gilardi, R. Angew. Chem. Int.
Ed. 2000, 39, 401. (b) Eaton, P. E.; Gilardi, R. L.; Zhang, M.
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1906, 73, 494.
A mixture of 14 (1.52 g, 6 mmol), NH2OH·HCl (1.25 g, 18 mmol),
NaOAc (1.48 g, 18 mmol) and MeOH (150 mL) was stirred under
reflux for 24 h. The reaction mixture was concentrated and the res-
idue was partitioned between CH2Cl2 (150 mL) and H2O (100 mL).
The organic layer was washed with brine (50 mL), dried over Na2-
SO4 and filtered. The solvent was removed under reduced pressure
and the residue was recrystallized (CH2Cl2–n-hexane) to provide
the corresponding oxime 15 as a white solid; yield: 1.56 g (92%).
Mp 209.8–210.5 °C.
(4) (a) Kaplan, R. B.; Shechter, H. J. Am. Chem. Soc. 1961, 83,
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(5) Archibald, T. G.; Baum, K. J. Org. Chem. 1988, 53, 4645.
(6) Dave, P. R.; Axenrod, T.; Qi, L.; Bracuti, A. J. Org. Chem.
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(7) (a) Moiseev, I. K.; Mratkhuzina, T. A.; Balenkova, E. S.;
Makarova, N. V. Russ. J. Org. Chem. 1999, 35, 839.
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FTIR: 3285, 2945, 1671, 1581, 1458, 1361, 957, 839 cm–1.
1H NMR (500 MHz, DMSO-d6): δ = 11.19–11.15 (m, 2 H), 4.81–
4.73, 3.89–3.85 (m, 2 H), 3.54, 2.68 (m, 2 H), 2.19–2.15, 2.08–1.97
(m, 2 H), 1.93–1.68 (m, 4 H).
13C NMR (125 MHz, DMSO-d6): δ = 155.2, 153.8, 122.2, 122.1,
42.6, 42.4, 41.1, 38.8, 36.4, 35.4, 35.1, 34.8, 34.5, 33.8, 33.7, 33.2,
32.9, 26.8, 26.7.
Anal. Calcd for C10H12N4O6: C, 42.26; H, 4.26; N, 19.71. Found: C,
42.37; H, 4.32; N, 19.59.
2,2,4,4,6,6-Hexanitroadamantane (1)9a
(Caution: N2O5 is a strong oxidizing agent that forms explosive
mixtures with organic compounds. The decomposition of N2O5 pro-
duces highly toxic NO2 gas. N2O5 must be handled in closed sys-
tems under a well-ventilated hood.) A mixture of 15 (1.2 g, 4.2
mmol), urea (0.76 g, 12.6 mmol), 4 Å molecular sieves (10 g) and
CH2Cl2 (100 mL) was stirred and heated to 50 °C. A solution of
N2O5 (1.36 g, 12.6 mmol) in CH2Cl2 (5 mL) was added dropwise
over 5 min, during which time a green color occurred initially and
then faded as more N2O5 was added. The reaction mixture was
stirred for an additional 30 min, then poured into an iced sat. solu-
tion of NaHCO3 (100 mL). The organic layer was washed with brine
(50 mL), dried over Na2SO4 and filtered. The solvent was removed
under reduced pressure, and the residue was purified by flash silica
gel column chromatography (EtOAc–PE, 1:12) to afford the desired
product 1 as a white solid (0.6 g, 35%), 4,4,6,6-tetranitroadaman-
tan-2-one (16) as a white solid (0.56 g, 40%) and dione 14 as a white
solid (0.16 g, 15%). Oximation and nitration of 16 according to the
above-described procedure for 14 gave the target product 1 as a
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Synthesis 2014, 46, 2225–2233
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