890
V. A. Zapol’skii et al.
PAPER
IR (KBr): 3073, 2972, 1665, 1581, 1349, 1291, 1266, 1155, 1125,
1083, 1039, 941, 922, 884, 838, 795, 701, 643, 614, 480 cm–1.
1-(1H-Benzotriazol-1-yl)-2-chloro-1-[(4-iodophenyl)imino]-2-
nitroethane (7)
Following typical procedure I (r.t., 1 d) gave 7 as a yellow solid;
yield: 3.26 g (74%); mp 119–120 °C.
1H NMR (400 MHz, CDCl3): d = 8.39 (d, J = 8.2 Hz, 1 H), 8.17 (d,
J = 8.2 Hz, 1 H), 7.69 (t, J = 8.0 Hz, 1 H), 7.55 (t, J = 8.0 Hz, 1 H),
7.12–7.28 (m, 2 H), 7.03–7.11 (m, 2 H), 7.01 (s, 1 H, CHCl).
IR (KBr): 3443, 2966, 1667, 1581, 1487, 1479, 1408, 1347, 1324,
1293, 1069, 1040, 1008, 921, 883, 785, 769, 746, 727, 496, 426
cm–1.
1H NMR (400 MHz, CDCl3): d = 8.37 (d, J = 8.0 Hz, 1 H), 8.18 (d,
J = 8.0 Hz, 1 H), 7.81 (d, J = 8.5 Hz, 2 H), 7.69 (t, J = 8.0 Hz, 1 H),
7.56 (t, J = 8.0 Hz, 1 H), 6.95 (s, 1 H, CHCl), 6.87 (d, J = 8.5 Hz, 2
H).
13C NMR (100 MHz, CDCl3): d = 146.2 (C1), 144.1 (Cq), 143.6
(Cq), 139.0 (2 CH, m-CPh), 131.0 (Cq), 130.4 (CH), 126.6 (CH),
121.7 (2 CH, o-CPh), 120.6 (CH), 114.8 (CH), 90.6 (CI), 79.5 (C2).
MS (DCP, 70 eV): m/z (%) = 441 (20) [M]+, 331 (5) [M – NO2 – N2
– HCl]+, 277 (36)[M – Bzt – NO2]+, 229 (7) [M – Bzt –
CH(NO2)Cl]+, 205 (100) [M – NO2 – N2 – I – Cl]+.
13C NMR (100 MHz, CDCl3): d = 161.4 (d, 1JC,F = 246.5 Hz, CF),
4
146.2 (C1), 143.8 (Cq), 140.5 (d, JC,F = 3.1 Hz, Cq,Ph), 131.0 (Cq),
3
130.4 (CH), 126.5 (CH), 121.5 (2 CH, d, JC,F = 8.1 Hz, o-CPh),
2
120.5 (CH), 117.0 (2 CH, d, JC,F = 22.6 Hz, m-CPh), 114.8 (CH),
79.4 (C2).
MS (DCP, 70 eV): m/z (%) = 333 (26) [M]+, 259 (10) [M – NO2 –
N2]+, 239 (10) [M – NO2CHCl]+, 223 (100) [M – NO2 – HCl – N2]+,
169 (80) [M – Bzt – NO2]+.
HRMS (EI): m/z [M]+ calcd for C14H9ClFN5O2: 333.0429; found:
333.0431.
1-(1H-Benzotriazol-1-yl)-2-chloro-1-[(4-chlorophenyl)imino]-
2-nitroethane (5)
Following typical procedure I (r.t., 6 h) gave 5 as a white solid;
yield: 3.25 g (93%); mp 133–134 °C.
HRMS (EI): m/z [M]+ calcd for C14H9ClIN5O2: 440.9490; found:
440.9493.
IR (KBr): 3424, 2951, 1666, 1580, 1486, 1449, 1402, 1349, 1292,
1076, 1039, 1010, 889, 883, 786, 771, 754, 725 cm–1.
1-(1H-Benzotriazol-1-yl)-2-chloro-1-[(4-methylphenyl)imino]-
2-nitroethane (8)
Following typical procedure I (–10 °C, 1 h, r.t., 6 h) gave 8 as a
yellowish solid; yield: 2.86 g (87%); mp 85–86 °C.
1H NMR (400 MHz, CDCl3): d = 8.37 (d, J = 8.0 Hz, 1 H), 8.17 (d,
J = 8.0 Hz, 1 H), 7.69 (t, J = 8.0 Hz, 1 H), 7.56 (t, J = 8.0 Hz, 1 H),
7.47 (d, J = 8.7 Hz, 2 H), 7.06 (d, J = 8.7 Hz, 2 H), 6.98 (s, 1 H,
CHCl).
IR (KBr): 3440, 2960, 1662, 1583, 1504, 1487, 1404, 1348, 1292,
1016, 921, 883, 821, 791, 773, 748, 705, 486 cm–1.
13C NMR (100 MHz, CDCl3): d = 146.2 (Cq), 143.6 (C1), 143.0
(Cq), 132.0 (CCl), 131.0 (Cq), 130.4 (CH), 130.2 (2 CH, m-CPh),
126.5 (CH), 121.2 (2 CH, o-CPh), 120.6 (CH), 114.8 (CH), 79.5
(C2).
1H NMR (400 MHz, CDCl3): d = 8.41 (d, J = 8.1 Hz, 1 H), 8.16 (d,
J = 8.1 Hz, 1 H), 7.67 (t, J = 8.1 Hz, 1 H), 7.54 (t, J = 8.1 Hz, 1 H),
7.30 (d, J = 8.0 Hz, 2 H), 7.02 (s, 1 H, CHCl), 7.00 (d, J = 8.0 Hz, 2
H), 2.41 (s, 3 H, Me).
MS (DCP, 70 eV): m/z (%) = 349 (24) [M]+, 275 (8) [M – NO2 –
N2]+, 239 (98) [M – NO2 – N2 – HCl]+, 205 (100) [M – NO2 – N2 –
2 Cl]+, 185 (65) [M – Bzt – NO2]+.
HRMS (EI): m/z [M]+ calcd for C14H9Cl2N5O2: 349.0130; found:
349.0130.
13C NMR (100 MHz, CDCl3): d = 146.1 (C1), 143.3 (Cq), 142.1
(Cq), 136.3 (Cq-Me), 131.1 (Cq), 130.6 (2 CH, m-CPh), 130.2 (CH),
126.6 (CH), 120.4 (CH), 119.6 (2 CH, o-CPh), 114.9 (CH), 79.4
(C2).
MS (DCP, 70 eV): m/z (%) = 329 (17) [M]+ (17), 235 (5) [M –
CH(NO2)Cl]+, 219 (77) [M – NO2 – N2 – HCl]+, 205 (20) [M – NO2
– N2 – Me – Cl]+, 165 (100) [M – Bzt – NO2]+.
1-(1H-Benzotriazol-1-yl)-1-[(4-bromophenyl)imino]-2-chloro-
2-nitroethane (6)
Following typical procedure I (r.t., 1 d) gave 6 as a white solid;
yield: 3.14 g (80%); mp 137–138 °C.
HRMS (EI): m/z [M]+ calcd for C15H12ClN5O2: 329.0679; found:
329.0681.
IR (KBr): 3442, 2945, 1666, 1578, 1483, 1450, 1408, 1398, 1369,
1073, 1038, 1009, 883, 829, 785, 771, 753, 724, 701 cm–1.
1-(1H-Benzotriazol-1-yl)-2-chloro-2-nitro-1-[(4-nitrophe-
nyl)imino]ethane (9)
Following typical procedure I (r.t., 1 h, reflux, 10 h) gave 9 as a
yellow solid; yield: 2.45 g (68%); mp 141–142 °C.
1H NMR (400 MHz, CDCl3): d = 8.36 (d, J = 8.0 Hz, 1 H), 8.17 (d,
J = 8.0 Hz, 1 H), 7.69 (t, J = 8.0 Hz, 1 H), 7.61 (d, J = 8.7 Hz, 2 H),
7.56 (t, J = 8.0 Hz, 1 H), 7.01 (d, J = 8.7 Hz, 2 H), 6.97 (s, 1 H,
CHCl).
IR (KBr): 3102, 2966, 1670, 1588, 1511, 1487, 1418, 1343, 1110,
1061, 1035, 920, 890, 859, 775, 753, 717, 693, 666 cm–1.
13C NMR (100 MHz, CDCl3): d = 146.2 (Cq), 143.7 (Cq), 143.4
(Cq), 133.1 (2 CH, m-CPh), 131.0 (Cq), 130.4 (CH), 126.5 (CH),
121.5 (2 CH, o-CPh), 120.5 (CH), 119.7 (CBr), 114.8 (CH), 79.5
(C2).
1H NMR (400 MHz, CDCl3): d = 8.38 (d, J = 9.1 Hz, 2 H, m-HPh),
8.35 (d, J = 8.0 Hz, 1 H), 8.20 (d, J = 8.0 Hz, 1 H), 7.73 (t, J = 8.0
Hz, 1 H), 7.60 (t, J = 8.0 Hz, 1 H), 7.25 (d, J = 9.1 Hz, 2 H), 6.96 (s,
1 H, CHCl).
15N NMR (60.83 MHz, CDCl3): d = –10.7 (NO2), –77.1 (NAr), –
13C NMR (100 MHz, CDCl3): d = 149.7 (Cq), 146.4 (Cq), 145.7
(Cq), 143.8 (Cq), 130.9 (Cq), 130.8 (CH), 126.9 (CH), 125.8 (2 CH),
120.8 (CH), 120.5 (2 CH), 114.7 (CH), 80.0 (C2).
1
141.2 (N1Bzt); N2Bzt and N3Bzt were not detected applying H,15N-
HMBC that was optimized on 8 Hz long-range N,H-coupling.
MS (DCP, 70 eV): m/z (%) = 393 (35) [M]+, 299 (2) [M –
NO2CHCl]+, 282 (8) [M – HNO2 – N2 – HCl]+, 238 (14) [M – Ph-
Br]+, 229 (65) [M – Bzt – NO2]+, 205 (100) [M – NO2 – N2 – Br –
Cl]+.
MS (DCP, 70 eV): m/z (%) = 360 (7) [M]+, 266 (6) [M –
CH(NO2)Cl]+, 250 (10) [M – NO2 – N2 – HCl]+, 205 (100) [M – 2
NO2 – N2 – Cl]+, 196 (85) [M – Bzt – NO2]+.
HRMS (EI): m/z [M]+ calcd for C14H9ClN6O4: 360.0374; found:
360.0371.
HRMS (EI): m/z [M]+ calcd for C14H9BrClN5O2: 392.9628; found:
392.9630.
Synthesis 2012, 44, 885–894
© Thieme Stuttgart · New York