Synthesis and Properties of Energetic 1,2,4-Oxadiazoles
131.7, 131.2, 128.6, 125.0, 124.6 117.1 ppm. C14H8N4O5 (312.24):
calcd. C 53.85, H 2.58, N 17.94; found C 53.73, H 2.37, N 18.23.
2.3 Hz, 1 H), 8.83 (t, J = 1.8 Hz, 1 H), 8.61–8.56 (m, 1 H), 8.53–
8.48 (m, 1 H), 7.94 (t, J = 8.1 Hz, 1 H) ppm. 13C NMR (75 MHz,
[D6]DMSO): δ = 173.0, 167.2, 148.7, 148.3, 133.3, 131.4, 127.9,
127.0, 126.6, 125.7, 122.5, 121.7 ppm. HRMS (DART-TOF) m/z:
[M + NH4]+ calcd. for C14H11N6O7 375.0684; found 375.0676.
3-(2-Nitrophenyl)-5-(4-nitrophenyl)-1,2,4-oxadiazole (4f): Method
A, yield 88%, colorless prisms, m.p. 173–175 °C. 1H NMR
(300 MHz, [D6]DMSO): δ = 8.48 (d, J = 9.0 Hz, 2 H), 8.41 (d, J
= 8.4 Hz, 2 H), 8.22–8.18 (m, 1 H), 8.08–8.04 (m, 1 H), 8.00–7.89
(m, 2 H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 173.9, 166.4,
150.2, 148.5, 133.6, 133.1, 131.3, 129.6 (2 C), 128.1, 124.7 (3 C),
119.6 ppm. C14H8N4O5 (312.24): calcd. C 53.85, H 2.58, N 17.94;
found C 53.94, H 2.17, N 17.68.
3-(3,5-Dinitrophenyl)-5-(2-nitrophenyl)-1,2,4-oxadiazole
(4n):
Method A, yield 84%, off-white solids, m.p. 200–202 °C. 1H NMR
(300 MHz, [D6]DMSO): δ = 9.06–9.02 (m, 3 H), 8.34–8.24 (m, 2
H), 8.08–8.01 (m, 2 H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ
= 173.7, 165.8, 148.8, 148.0, 134.7, 134.1, 131.9, 128.2, 127.0, 125.1,
121.3, 116.9 ppm. C14H7N5O7 (357.24): calcd. C 47.07, H 1.98, N
19.60; found C 47.46, H 1.70, N 19.20.
5-(2-Nitrophenyl)-3-(3-nitrophenyl)-1,2,4-oxadiazole (4g): Method
A, yield 91%, colorless solids, m.p. 155–157 °C. 1H NMR
(300 MHz, [D6]DMSO): δ = 8.72 (s, 1 H), 8.47 (d, J = 8.7 Hz, 2
H), 8.32–8.24 (m, 1 H), 8.24–8.18 (m, 1 H), 8.06–7.97 (m, 2 H),
7.92 (t, J = 8.1 Hz, 1 H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ
= 173.2, 166.8, 148.2, 148.1, 134.5, 134.0, 133.1, 131.7, 131.4, 127.0,
126.5, 125.0, 121.6, 117.1 ppm. C14H8N4O5 (312.24): calcd. C
53.85, H 2.58, N 17.94; found C 53.87, H 2.24, N 17.79.
5-(3,5-Dinitrophenyl)-3-(2-nitrophenyl)-1,2,4-oxadiazole
(4o):
1
Method B, yield 62%, colorless solids, m.p. 205–207 °C. H NMR
(300 MHz, [D6]DMSO): δ = 9.13–9.08 (m, 3 H), 8.24–8.20 (m, 1
H), 8.12–8.08 (m, 1 H), 8.01–7.90 (m, 2 H) ppm. 13C NMR
(75 MHz, [D6]DMSO): δ = 172.5, 166.5, 148.7, 148.5, 133.7, 133.2,
131.4, 127.9, 125.4, 124.8, 122.5, 119.2 ppm. C14H7N5O7 (357.24):
calcd. C 47.07, H 1.98, N 19.60; found C 47.20, H 1.60, N 19.44.
3-(2-Nitrophenyl)-5-(3-nitrophenyl)-1,2,4-oxadiazole (4h): Method
A, yield 90%, colorless crystals, m.p. 161–162 °C. 1H NMR
(300 MHz, [D6]DMSO): δ = 8.79 (t, J = 2.0 Hz, 1 H), 8.60–8.57
(m, 1 H), 8.56–8.54 (m, 1 H), 8.21–8.17 (m, 1 H), 8.08–8.04 (m, 1
H), 8.00–7.89 (m, 3 H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ
= 173.8, 166.3, 148.5, 148.2, 133.9, 133.6, 133.0, 131.6, 131.3, 127.9,
124.7, 124.2, 122.5, 119.5 ppm. C14H8N4O5 (312.24): calcd. C
53.85, H 2.58, N 17.94; found C 53.93, H 2.21, N 17.78.
3-(2,4-Dinitrophenyl)-5-(4-nitrophenyl)-1,2,4-oxadiazole
(4p):
Method A, yield 82%, yellow solids, m.p. 171–173 °C. 1H NMR
(300 MHz, [D6]DMSO): δ = 8.99 (d, J = 2.4 Hz, 1 H), 8.72 (dd, J
= 8.7, 2.1 Hz, 1 H), 8.48 (d, J = 8.7 Hz, 2 H), 8.42 (d, J = 9.0 Hz,
2 H), 8.38 (d, J = 8.4 Hz, 1 H) ppm. 13C NMR (75 MHz, [D6]-
DMSO): δ = 174.4, 165.0, 150.2, 149.4, 148.5, 132.9, 129.7, 127.9,
127.8, 124.7, 124.3, 120.2 ppm. C14H7N5O7 (357.24): calcd. C
47.07, H 1.98, N 19.60; found C 47.41, H 1.66, N 19.31.
3,5-Bis(2-nitrophenyl)-1,2,4-oxadiazole (4i): Method A, yield 85%,
colorless solids, m.p. 162–164 °C. 1H NMR (300 MHz, [D6]-
DMSO): δ = 8.30–8.23 (m, 1 H), 8.20–8.11 (m, 2 H), 8.05–7.97 (m,
3 H), 7.96–7.88 (m, 2 H) ppm. 13C NMR (75 MHz, [D6]DMSO):
δ = 172.6, 166.1, 148.5, 148.1, 134.5, 133.9, 133.6, 133.1, 131.6,
131.3, 125.0, 124.8, 119.3, 116.9 ppm. C14H8N4O5 (312.24): calcd.
C 53.85, H 2.58, N 17.94; found C 54.01, H 2.17, N 18.02.
5-(2,4-Dinitrophenyl)-3-(4-nitrophenyl)-1,2,4-oxadiazole
(4q):
1
Method B, yield 64%, colorless solids, m.p. 181–183 °C. H NMR
(300 MHz, [D6]DMSO): δ = 9.04 (d, J = 2.1 Hz, 1 H), 8.78 (dd, J
= 8.7, 2.1 Hz, 1 H), 8.52 (d, J = 8.7 Hz, 1 H), 8.49–8.44 (m, 2 H),
8.36–8.30 (m, 2 H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ =
171.6, 167.2, 150.1, 149.5, 148.2, 133.5, 131.0, 128.6, 128.0, 124.7,
121.7, 120.3 ppm. HRMS (DART-TOF) m/z: (M + NH4)+ calcd.
for C14H11N6O7 375.0684; found 375.0685.
3-(3,5-Dinitrophenyl)-5-(4-nitrophenyl)-1,2,4-oxadiazole
(4j):
1
Method A, yield 94%, colorless solids, m.p. 248–249 °C. H NMR
(300 MHz, [D6]DMSO): δ = 9.08 (d, J = 2.1 Hz, 2 H), 9.03 (t, J =
2.1 Hz, 1 H), 8.52 (d, J = 8.4 Hz, 2 H), 8.47 (d, J = 9.0 Hz, 2 H)
ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 174.9, 166.0, 150.2,
148.8, 129.8, 128.5, 128.1, 126.9, 124.7, 121.2 ppm. C14H7N5O7
(357.24): calcd. C 47.07, H 1.98, N 19.60; found C 47.11, H 1.66,
N 19.28.
3-(2,4-Dinitrophenyl)-5-(3-nitrophenyl)-1,2,4-oxadiazole
(4r):
Method A, yield 81%, yellow solids, m.p. 190–192 °C. 1H NMR
(300 MHz, [D6]DMSO): δ = 8.99 (dd, J = 2.4, 0.9 Hz, 1 H), 8.82–
8.80 (m, 1 H), 8.74–8.70 (m, 1 H), 8.62–8.56 (m, 2 H), 8.39 (d, J
= 8.4 Hz, 1 H), 7.99 (t, J = 8.1 Hz, 1 H) ppm. 13C NMR (75 MHz,
[D6]DMSO): δ = 174.3, 164.9, 149.4, 148.5, 148.2, 134.1, 132.9,
131.6, 128.1, 127.8, 124.3, 124.0, 122.6, 120.2 ppm. C14H7N5O7
(357.24): calcd. C 47.07, H 1.98, N 19.60; found C 47.37, H 1.66,
N 19.35.
5-(3,5-Dinitrophenyl)-3-(4-nitrophenyl)-1,2,4-oxadiazole
(4k):
1
Method B, yield 63%, off-white solids, m.p. 234–236 °C. H NMR
(300 MHz, [D6]DMSO): δ = 9.17 (d, J = 1.8 Hz, 2 H), 9.10 (t, J =
2.1 Hz, 1 H), 8.45 (d, J = 8.7 Hz, 2 H), 8.41 (d, J = 9.3 Hz, 2 H)
ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 173.0, 167.3, 149.4,
148.7, 131.2, 128.7, 127.8, 125.7, 124.6, 122.4 ppm. HRMS (DIP/
CI-MS) m/z: [M + H]+ calcd. for C14H8N5O7 358.0424; found
358.0424.
5-(2,4-Dinitrophenyl)-3-(3-nitrophenyl)-1,2,4-oxadiazole
(4s):
1
Method B, yield 65%, colorless solids, m.p. 198–200 °C. H NMR
(300 MHz, [D6]DMSO): δ = 9.04 (d, J = 2.1 Hz, 1 H), 8.79–8.72
(m, 2 H), 8.55–8.47 (m, 3 H), 7.94 (t, J = 8.1 Hz, 1 H) ppm. 13C
NMR (75 MHz, [D6]DMSO): δ = 171.5, 167.0, 150.1, 148.3, 135.0–
128.0 (m), 126.7, 121.7, 121.1–119.1 (m) ppm. C14H7N5O7 (357.24):
calcd. C 47.07, H 1.98, N 19.60; found C 47.30, H 1.59, N 19.85.
3-(3,5-Dinitrophenyl)-5-(3-nitrophenyl)-1,2,4-oxadiazole
(4l):
1
Method A, yield 86%, colorless solids, m.p. 222–224 °C. H NMR
(300 MHz, [D6]DMSO): δ = 9.10 (s, 2 H), 9.04 (d, J = 0.6 Hz, 1
H), 8.90 (s, 1 H), 8.68 (d, J = 8.4 Hz, 1 H), 8.59 (d, J = 7.8 Hz, 1 H),
7.99 (t, J = 8.0 Hz, 1 H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ
= 174.8, 166.0, 148.8, 148.2, 134.2, 131.6, 128.5, 128.1, 126.9, 124.2,
122.7, 121.2 ppm. C14H7N5O7 (357.24): calcd. C 47.07, H 1.98, N
19.60; found C 47.38, H 1.69, N 19.35.
3-(2,4-Dinitrophenyl)-5-(2-nitrophenyl)-1,2,4-oxadiazole
(4t):
Method A, yield 80%, colorless microcrystals, m.p. 180–182 °C. 1H
NMR (300 MHz, [D6]DMSO): δ = 8.97 (d, J = 2.4 Hz, 1 H), 8.72
(ddd, J = 8.4, 2.3, 0.8 Hz, 1 H), 8.34 (d, J = 8.4 Hz, 1 H), 8.31–
8.25 (m, 1 H), 8.20–8.13 (m, 1 H), 8.06–7.99 (m, 2 H) ppm. 13C
NMR (75 MHz, [D6]DMSO): δ = 173.2, 164.8, 149.4, 148.5, 148.0,
5-(3,5-Dinitrophenyl)-3-(3-nitrophenyl)-1,2,4-oxadiazole
Method B, yield 60%, off-white solids, m.p. 221–223 °C. H NMR
(4m): 134.7, 134.1, 132.9, 131.8, 127.9, 125.1, 124.1, 120.3, 116.7 ppm.
1
HRMS (DART-TOF) m/z: [M + NH4]+ calcd. for C14H11N6O7
(300 MHz, [D6]DMSO): δ = 9.19 (d, J = 2.1 Hz, 2 H), 9.10 (t, J =
375.0684; found 375.0667.
Eur. J. Org. Chem. 2015, 7468–7474
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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