DOI: 10.1039/C7OB00715A
Organic & Biomolecular Chemistry
7-Methyl-5H-benzo[6,7]indolo[3',2':4,5]oxepino[2,3-
b]quinoxaline (3b)
Light brown solid; Yield: 85%; mp: 282-284 °C; Rf =0.5 (20%
152.7, 145.1, 141.4, 139.3, 138.0, 135.0, 133.8, 130.0 (2C), 129.6,
128.5, 128.1, 126.8, 126.3, 125.1, 124.7, 122.5, 121.9, 118.9,
112.5, 111.3; Mass: m/z (CI) 414 (M + 1, 100%). HRMS (ESI):
EtOAc/ n-hexane); IR: 3302, 2922, 1453, 1224, 756 cm−1; 1H 60 m/z calcd for C22H13OBrN3 ([M + H]+) 414.0237, found 414.0229.
5
NMR (400 MHz, DMSO-d6): δ 12.31 (s, 1H), 8.56 (d, J= 7.6 Hz,
1H), 8.12 (d, J=8 Hz, 1H), 7.96 (d, J=8 Hz, 1H), 7.79-7.72 (m, 3H),
7.55 (d, J=8 Hz, 1H), 7.46 (d, J=7.6 Hz, 1H), 7.36-7.26 (m, 3H),
2.39 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ 155.2, 151.6,
2-Methyl-5H-benzo[6,7]indolo[3',2':4,5]oxepino[2,3-
b]quinoxaline (3f)
Light brown solid; Yield: 85%; mp: 210-213 °C; Rf = 0.4 (20%
145.6, 141.3, 139.2, 138.0, 136.9, 136.1, 131.9, 129.8, 129.4, 65 EtOAc/ n-hexane); IR: 3389, 2920, 1502, 1448, 1220, 746 cm−1;
10 128.4, 128.1, 128.0, 126.9, 124.2, 123.8, 122.7, 122.3, 121.7,
112.4, 110.6, 20.9; Mass ; m/z (CI) 350 (M + 1, 100%); HRMS
(ESI): m/z calcd for C23H16ON3 ([M + H]+) 350.1287, found
350.1300.
7-Chloro-5H-benzo[6,7]indolo[3',2':4,5]oxepino[2,3-
15 b]quinoxaline (3c)
Yellow solid; Yield: 85%; mp: 272-274 oC; Rf = 0.6 (20% EtOAc/
n-hexane); IR: 3445, 2921, 1533, 1464, 1220, 771 cm−1; 1H NMR
(400 MHz, DMSO-d6): δ 12.41 (s, 1H), 8.57 (d, J= 7.6 Hz, 1H),
8.10 (d, J= 8 Hz, 1H), 7.93 (d, J= 7.6 Hz, 2H), 7.80-7.70 (m, 2H),
20 7.61-7.56 (m, 3H), 7.34 (t, J=7.6 Hz, 1H), 7.28 (t, J= 7.6 Hz, 1H);
13C NMR (100 MHz, DMSO-d6): δ 154.8, 152.2, 145.0, 141.3,
139.2, 138.0, 135.1, 130.9 (2C), 130.0, 129.7, 128.5, 128.1, 127.2,
126.7, 125.9, 124.8, 124.7, 122.5, 121.9, 112.5, 111.3; Mass: m/z
1H NMR (400 MHz, DMSO-d6): δ 12.23 (s, 1H), 8.37 (s, 1H), 8.13
(d, J=8 Hz, 1H), 7.94 (d, J=8 Hz, 1H), 7.86 (d, J=7.6 Hz, 1H), 7.79-
7.70 (m, 2H), 7.59-7.52 (m, 2H), 7.46 (d, J= 8.4 Hz, 2H), 7.15 (d,
J= 8.4 Hz, 1H), 2.48 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ
70 155.1, 153.6, 145.6, 141.3, 139.2, 136.7, 136.3, 131.4, 130.5,
129.8, 129.4, 128.5, 128.1, 127.8, 127.2, 126.9, 125.9, 124.3,
123.0, 121.9, 112.1, 110.2, 22.0; Mass: m/z (CI) 350 (M+1,
100%); HRMS (ESI): m/z calcd for C23H16ON3 ([M + H]+)
350.1287, found 350.1287.
75
13,14-Dimethyl-5H-benzo[6,7]indolo[3',2':4,5]oxepino[2,3-
b]quinoxaline (3g)
o
Dark brown solid; Yield: 78%; mp: 255-27 C; Rf = 0.4 (20%
EtOAc/ n-hexane); IR: 3396, 2923, 1537, 1502, 1215, 745, 667
(CI) 370 (M + 1, 100%); HPLC: 97.60%, column: X-Select C-18 80 cm−1; 1H NMR (400 MHz, DMSO-d6) δ 12.30 (s, 1H), 8.56 (d, J=
25 (4.6 × 150 mm) 5µm, mobile phase A: 5µm Ammonium Acetate
in water, mobile phase B: ACN T/%B: 0/5, 3/5, 9/50, 14/80, 19/95,
23/5, 25/5; flow rate: 1.0 mL/min, Diluent: ACN : Water (80 : 20);
UV 250 nm, retention time 18.43 min; HRMS (ESI): m/z calcd for
C19H14ON3 ([M + H]+) 370.0742, found 370.075.
30
7.6 Hz, 1H), 7.90-7.86 (m, 2H), 7.71 (s, 1H), 7.57-7.51 (m, 3H),
7.45 (t, J= 7.2 Hz, 1H), 7.30 (t, J=7.2 Hz, 1H), 7.25 (t, J=7.2 Hz,
1H), 2.44 (s, 3H), 2.43 (s, 3H); 13C NMR (100 MHz, DMSO-d6):
δ 154.7, 153.8, 144.3, 140.1, 139.8, 139.6, 138.0, 137.9, 136.2,
85 131.4, 127.8, 127.6, 127.2, 126.9, 126.8, 124.3, 124.1, 123.0,
122.3, 121.6, 112.3, 110.8, 20.2, 20.1; Mass: m/z (CI) 364 (M+1,
100%); HRMS (ESI): m/z calcd for C24H18N3O ([M + H]+)
364.1444, found 364.1458.
6,8-Dichloro-5H-benzo[6,7]indolo[3',2':4,5]oxepino[2,3-
b]quinoxaline (3d)
Brown solid; Yield: 81%; mp: 170 oC (decomposed); Rf = 0.5 (10%
EtOAc/ n-hexane); IR: 3300, 2921, 1542, 1448, 1214, 747, 667 90 7,13,14-Trimethyl-5H-benzo[6,7]indolo[3',2':4,5]oxepino[2,3-
35 cm−1; 1H NMR (400 MHz, DMSO-d6): δ 12.45 (s, 1H), 8.59 (d, J=
8 Hz, 1H), 8.15 (d, J= 8 Hz, 1H), 7.97 (d, J= 8 Hz, 1H), 7.92 (d,
J= 2.4 Hz, 1H), 7.87 (d, J= 2.4 Hz, 1H), 7.81-7.73 (m, 2H), 7.58
(d, J= 8.4 Hz, 1H), 7.36 (t, J= 7.6 Hz, 1H), 7.32 (t, J= 8 Hz, 1H);
b]quinoxaline (3h)
Off white solid; Yield: 78%; mp: 258-261 °C; Rf = 0.5 (20%
EtOAc/ n-hexane); IR: 3350, 2924, 1507, 1214, 750, 667 cm−1; 1H
NMR (400 MHz, DMSO-d6) δ 12.23 (s, 1H), 8.55 (d, J= 7.6 Hz,
13C NMR (100 MHz, DMSO-d6): δ 154.5, 147.8, 144.7, 141.4, 95 1H), 7.88 (s, 1H), 7.68 (d, J=6.8 Hz, 2H), 7.55 (d, J=8 Hz, 1H),
40 139.2, 138.0, 134.3, 130.9, 130.4, 130.3, 129.9, 128.6, 128.4,
128.3, 127.4, 126.6, 126.1, 124.9, 122.6, 122.1, 112.6, 111.6;
Mass: m/z (CI) 404 (M + 1, 100%); HPLC: 95.4%, Column: X-
Select C18 (4.6X150mm) 5micron, mobile phase A: 10 mM
7.44 (d, J=8.4 Hz, 1H), 7.33-7.21 (m, 3H), 2.44 (s, 3H), 2.42 (s,
3H), 2.38 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ 154.8, 151.8,
144.4, 140.1, 139.8, 139.6, 137.9 (2C), 136.4, 136.0, 131.8, 128.0,
127.7, 127.2, 126.9, 124.1, 123.9, 122.6, 122.3, 121.5, 112.3,
Ammoniumacetate in Mli-Q-water, mobile phase B: 100% 100 110.8, 20.9, 20.2, 20.1; Mass : m/z (CI) 378 ((M+1, 100%); HRMS
45 Acetonitrile, Gradient Time%B: 0/5, 1.5/5, 5/50, 9/80, 16/95,
19/95, 21/5. Column Temp: 30 oC, flow rate: 1.0 mL/min, Diluent
: ACN : Mli-Q-water (80:20)v/v.
(ESI): m/z calcd for C25H20ON3 ([M + H]+) 378.1600, found
378.1617.
6,8-Dichloro-13,14-dimethyl-5H-
7-Bromo-5H-benzo[6,7]indolo[3',2':4,5]oxepino[2,3-
50 b]quinoxaline (3e)
Yellow solid; Yield: 81%; mp: 265-268 °C; Rf = 0.4 (20% EtOAc/
n-hexane); IR: 3419, 2921, 1541, 1449, 1223, 1086, 751 cm−1; 1H
NMR (400 MHz, DMSO-d6): δ 12.40 (s, 1H), 8.57 (d, J=8 Hz, 1H),
105 benzo[6,7]indolo[3',2':4,5]oxepino[2,3-b]quinoxaline (3i)
Pale yellow solid; Yield: 78%; mp: 312-315 °C; Rf = 0.5 (10%
EtOAc/ n-hexane); IR: 3441, 2918, 1453, 1225, 1009, 844, 748
cm−1; 1H NMR (400 MHz, DMSO-d6) δ 12.40 (s, 1H), 8.58 (d, J=
8 Hz, 1H), 7.95-7.88 (m, 3H), 7.77 (s, 1H), 7.57 (d, J= 8.4, 1H),
8.11 (d, J=8.4 Hz, 1H), 8.08 (d, J= 2.4 Hz, 1H), 7.95 (d, J= 8 Hz, 110 7.38 (t, J=7.2, 1H), 7.29 (t, J=7.6 Hz, 1H), 2.44 (s, 3H), 2.45 (s,
55 1H), 7.80-7.69 (m, 3H), 7.57-7.52 (m, 2H), 7.34 (t, J= 7.2 Hz, 1H),
7.27 (t, J= 7.2 Hz, 1H); 13C NMR (100 MHz, DMSO-d6): δ 154.8,
3H); 13C NMR (400 MHz, DMSO-d6): δ 154.0, 147.9, 143.5,
140.3, 140.2 (2C), 138.0, 137.9, 133.8, 130.8, 130.2, 128.4, 127.7,
Org. Biomol. Chem.,