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Can. J. Chem. Vol. 92, 2014
113.9, 113.8, 113.0, 101.4, 99.4, 67.9. MS (ESI): 439 (M+H+, 100). Anal.
calcd. for C27H14N6O: C 73.96, H 3.22, N 19.17; found: C 73.63, H
3.49, N 18.84.
2,2=-Diphenyl-2,3=-biindolin-3-one (7b)
Straw yellow amorphous solid. IR (KBr) max: 3427, 3312, 1673,
1
1610, 1151, 754 cm−1. H NMR (400 MHz, DMSO-d6) ␦: 11.36 (s, 1H,
NH), 8.35 (s, 1H, NH), 7.51 (dt, J = 8.1, 1.0 Hz, 1H, Ar-H), 7.38 (m, 2H,
Ar-H), 7.34 (d, J = 8.1 Hz, 1H, Ar-H), 7.25 (d, J = 7.6 Hz, 1H, Ar-H), 7.15
(m, 3H, Ar-H), 7.05 (m, 6H, Ar-H), 6.98 (d, J = 8.1 Hz, 1H, Ar-H), 6.76
(t, J = 7.6 Hz, 1H, Ar-H), 6.71 (t, J = 7.6 Hz, 1H, Ar-H), 6.61 (d, J = 8.1 Hz,
1H, Ar-H). 13C NMR (100 MHz, DMSO-d6) ␦: 200.9, 160.5, 140.3, 138.4,
137.9, 136.2, 133.6, 130.0, 128.0, 127.9, 127.8, 127.6, 127.5, 127.4,
124.8, 121.6, 120.8, 119.1, 119.0, 117.9, 112.4, 111.7, 111.5, 71.6. MS (ESI):
401 (M+H+, 100). Anal. calcd. for C28H20N2O: C 83.98, H 5.03, N 7.00;
found: C 84.05, H 4.72, N 6.81.
6,6=-Dichloro-2-(6-chloro-1H-indol-3-yl)-2,3=-biindolin-3-one (6k)
Yellow solid, mp 197–199 °C (from EtOAc−PE = 1:2). IR (KBr)
:
max
3412, 1668, 1611, 1452, 804 cm−1. 1H NMR (400 MHz, CDCl3) ␦: 8.43 (s,
2H, NH), 8.50 (s, 1H, NH), 7.66 (d, J = 7.6 Hz, 1H, Ar-H), 7.57 (d, J =
7.6 Hz, 1H, Ar-H), 7.31 (d, J = 8.0 Hz, 2H, Ar-H), 7.19 (s, 1H, Ar-H), 7.17
(s, 1H, Ar-H), 7.18 (d, J = 7.6 Hz, 2H, Ar-H), 6.94 (t, J = 8.0 Hz, 2H,
Ar-H), 6.89 (t, J = 7.6 Hz, 1H, Ar-H), 5.60 (s, 1H, NH). 13C NMR
(100 MHz, CDCl3) ␦: 199.5, 161.1, 142.9, 137.8, 126.8, 126.5, 125.6,
124.6, 122.0, 119.4, 118.1, 116.7, 114.1, 111.8, 111.5, 68.2. MS (ESI): 466
(M+H+, 100), 468 (M+H+, 100), 470 (M+H+, 30). Anal. calcd. for
C24H14Cl3N3O1: C 61.76, H 3.02, N 9.00; found: C 62.08, H 2.84, N
8.75.
1,1=-Dimethyl-2,2=-diphenyl-2,3=-biindolin-3-one (7c)
Straw yellow amorphous solid. IR (KBr) max: 3440, 1616,
1123 cm−1. 1H NMR (400 MHz, CDCl3) ␦: 7.42 (dt, J = 1.3, 8.4 Hz, 2H,
Ar-H), 7.35 (d, J = 8.2 Hz, 2H, Ar-H), 7.31–7.25 (s, 4H, Ar-H), 7.24–7.18
(s, 3H, Ar-H), 7.13 (d, J = 7.2 Hz, 1H, Ar-H), 6.93 (dt, J = 1.3, 7.6 Hz, 1H,
Ar-H), 6.91 (dt, J = 1.3, 7.2 Hz, 1H, Ar-H), 6.82 (d, J = 7.6 Hz, 1H, Ar-H),
6.65 (d, J = 8.2 Hz, 1H, Ar-H), 6.58 (d, J = 8.4 Hz, 1H, Ar-H), 6.55 (t, J =
7.2 Hz, 1H, Ar-H), 3.47 (s, 3H, CH3), 2.80 (s, 3H, CH3). 13C NMR
(100 MHz, CDCl3) ␦: 200.1, 159.4, 140.0, 138.5, 137.2, 136.9, 131.4,
131.3, 130.7, 128.3, 128.2, 127.7, 127.6, 126.9, 125.2, 121.9, 121.5, 119.5,
119.4, 116.4, 109.8, 109.4, 107.7, 76.2, 30.5, 29.6. MS (ESI): 429 (M+H+,
100). Anal. calcd. for C30H24N2O: C 84.08, H 5.65, N 6.54; found: C
83.87, H 5.96, N 6.25.
7,7=-Dimethoxy-2-(7-methoxy-1H-indol-3-yl)-2,3=-biindolin-
3-one (6o)
Yellow solid, mp 209–210 °C (from EtOAc−PE = 1:2). IR (KBr)
:
max
3406, 1660, 1615, 1452, 1116, 1061 cm−1. 1H NMR (400 MHz, CDCl3) ␦:
8.30 (s, 2H, NH), 7.37 (d, J = 7.8 Hz, 1H, Ar-H), 7.16 (s, 1H, Ar-H), 7.15
(s, 1H, Ar-H), 7.05 (d, J = 8.1 Hz, 2H, Ar-H), 6.99 (d, J = 7.8 Hz, 1H,
Ar-H), 6.92 (t, J = 8.1 Hz, 2H, Ar-H), 6.86 (t, J = 7.8 Hz, 1H, Ar-H), 6.62
(d, J = 7.8 Hz, 2H, Ar-H), 5.58 (s, 1H, NH), 3.95 (s, 6H, 2 × OCH3), 3.88
(s, 3H, OCH3). 13C NMR (100 MHz, CDCl3) ␦: 201.0, 151.9, 146.7, 146.2,
127.6, 127.1, 123.5, 120.6, 120.2, 119.3, 116.7, 115.8, 115.7, 113.3, 102.0,
68.6, 55.4, 55.3. MS (ESI): 454 (M+H+, 100). Anal. calcd. for
C27H23N3O4: C 71.51, H 5.11, N 9.27; found: C 71.43, H 5.30, N 8.92.
Diethyl 3-oxo-2,3=-biindoline-2,2=-dicarboxylate (7d)
Straw yellow amorphous solid. IR (KBr) max: 3416, 1728, 1688,
1612, 1264, 1143 cm−1. 1H NMR (400 MHz, CDCl3) ␦: 9.10 (s, 1H, NH),
7.79 (d, J = 7.5 Hz, 1H, Ar-H), 7.52 (t, J = 8.6 Hz, 1H, Ar-H), 7.49 (d, J =
8.6 Hz, 1H, Ar-H), 7.39 (d, J = 8.3 Hz, 1H, Ar-H), 7.28 (t, J = 7.4 Hz, 1H,
Ar-H), 7.05 (t, J = 7.4 Hz, 1H, Ar-H), 6.96 (d, J = 8.3 Hz, 1H, Ar-H), 6.95
(t, J = 7.4 Hz, 1H, Ar-H), 5.98 (s, 1H, NH), 4.35 (q, J = 7.1 Hz, 2H, OCH2),
4.25 (q, J = 7.1 Hz, 2H, OCH2), 1.38 (t, J = 7.1 Hz, 3H, CH3), 1.21 (t, J =
7.1 Hz, 3H, CH3). 13C NMR (100 MHz, CDCl3) ␦: 194.9, 168.2, 161.9,
138.0, 135.7, 130.1, 128.4, 125.7, 125.5, 125.4, 125.3, 122.3, 121.2, 120.0,
119.9, 113.1, 112.0, 72.8, 62.8, 61.5, 14.3, 13.9. MS (ESI): 393 (M+H+,
100). Anal. calcd. for C22H20N2O5: C 67.34, H 5.14, N 7.14; found: C
67.68, H 4.83, N 6.91.
7,7=-Dinitro-2-(7-nitro-1H-indol-3-yl)-2,3=-biindolin-3-one (6p)
Yellow solid, mp 302–305 °C (from EtOAc−PE = 1:2). IR (KBr)
max: 3411, 1630, 1513, 1478, 1309 cm−1. 1H NMR (400 MHz, CDCl3) ␦:
10.07 (s, 2H, NH), 8.47 (dd, J = 7.5, 2.2 Hz, 1H, Ar-H), 8.19 (d, J = 8.0 Hz,
2H, Ar-H), 8.08 (d, J = 7.5 Hz, 1H, Ar-H), 7.92 (s, 1H, NH), 7.76 (d, J =
8.0, Hz, 2H, Ar-H), 7.47 (d, J = 2.2 Hz, 2H, Ar-H), 7.15 (t, J = 8.0 Hz, 2H,
Ar-H), 7.05 (t, J = 7.5 Hz, 1H, Ar-H). 13C NMR (100 MHz, CDCl3) ␦:
196.6, 152.0, 133.4, 133.0, 131.9, 130.5, 128.7, 128.5, 126.1, 126.0,
122.9, 120.1, 120.0, 118.5, 115.0, 67.7. MS (ESI): 499 (M+H+, 100), 521
(M+Na+, 20). Anal. calcd. for C24H14N6O7: C 57.84, H 2.83, N 16.86;
found: C 60.03, H 2.52, N 16.67.
Diethyl 5,5=-dichloro-3-oxo-2,3=-biindoline-2,2=-dicarboxylate (7e)
Straw yellow amorphous solid. IR (KBr) max: 3428, 1725, 1705,
1615, 1252, 1139 cm−1. 1H NMR (400 MHz, DMSO-d6) ␦: 12.38 (s, 1H,
NH), 8.27 (s, 1H, NH), 7.64 (d, J = 2.2 Hz, 1H, Ar-H), 7.55 (dd, J = 8.8,
2.2 Hz, 1H, Ar-H), 7.50 (d, J = 8.8 Hz, 1H, Ar-H), 7.26 (dd, J = 8.8,
3.0 Hz, 1H, Ar-H), 7.21 (d, J = 3.0 Hz, 1H, Ar-H), 7.02 (d, J = 8.8 Hz, 1H,
Ar-H), 4.30 (q, J = 7.1 Hz, 2H, OCH2), 4.08 (q, J = 7.1 Hz, 2H, OCH2),
1.30 (t, J = 7.1 Hz, 3H, CH3), 1.07 (t, J = 7.1 Hz, 3H, CH3). 13C NMR
(100 MHz, DMSO-d6) ␦: 194.4, 167.6, 161.3, 161.2, 138.5, 134.7, 127.8,
125.9, 125.3, 125.2, 123.9, 122.7, 120.5, 119.2, 115.2, 114.9, 114.7, 73.5,
62.3, 61.6, 14.5, 14.2. MS (ESI): 461 (M+H+, 100), 463 (M+H+, 60). Anal.
calcd. for C22H18Cl2N2O5: C 57.28, H 3.93, N 6.07; found: C 56.96, H
4.11, N 5.79.
1,1=-Diethyl-2-(1-ethyl-1H-indol-3-yl)-2,3=-biindolin-3-one (6s)
Yellow solid, mp 238–241 °C (from EtOAc−PE = 1:2). IR (KBr)
:
max
3413, 1699, 1609, 1486, 1463, 740 cm−1. 1H NMR (400 MHz, CDCl3) ␦:
7.69 (d, J = 7.4 Hz, 1H, Ar-H), 7.56 (dt, J = 8.3, 1.2 Hz, 1H, Ar-H), 7.35
(t, J = 7.9 Hz, 4H, Ar-H), 7.18 (t, J = 7.9 Hz, 2H, Ar-H), 7.06 (s, 2H,
Ar-H), 6.97 (t, J = 7.4 Hz, 2H, Ar-H), 6.86 (d, J = 8.3 Hz, 1H, Ar-H), 6.76
(t, J = 7.4 Hz, 1H, Ar-H), 4.13 (q, J = 7.3 Hz, 4H, 2 × CH2), 3.59 (q, J =
7.1 Hz, 2H, CH2), 1.43 (t, J = 7.3 Hz, 6H, 2 × CH3), 0.67 (t, J = 7.1 Hz, 3H,
CH3). 13C NMR (100 MHz, CDCl3) ␦: 200.7, 158.7, 137.5, 136.7, 128.2,
126.6, 125.9, 121.8, 121.5, 119.2, 118.7, 116.4, 111.9, 109.3, 108.0, 72.7,
41.0, 38.2, 15.5, 13.3. MS (ESI): 448 (M+H+, 100). Anal. calcd. for
C30H29N3O: C 80.51, H 6.53, N 9.39; found: C 80.17, H 6.74, N 9.25.
2,2=-Dimethyl-2,3=-biindolin-3-one (7a)
2,2=,5,5=-Tetramethyl-2,3=-biindolin-3-one (7f)
Straw yellow amorphous solid. IR (KBr) max: 3425, 1672, 1614,
1117 cm−1. 1H NMR (400 MHz, DMSO-d6) ␦: 7.99 (s, 1H, NH), 7.72 (d,
J = 7.7 Hz, 1H, Ar-H), 7.53 (dt, J = 1.0, 8.5 Hz, 1H, Ar-H), 7.38 (d, J =
8.1 Hz, 1H, Ar-H), 7.24 (d, J = 8.1 Hz, 1H, Ar-H), 7.07 (dt, J = 1.0, 8.1 Hz,
1H, Ar-H), 6.96 (dt, J = 1.0, 8.1 Hz, 1H, Ar-H), 6.89 (t, J = 7.7 Hz, 1H,
Ar-H), 6.88 (d, J = 8.5 Hz, 1H, Ar-H), 5.30–4.80 (s, 1H, NH), 2.36 (s, 3H,
CH3), 1.93 (s, 3H, CH3). 13C NMR (100 MHz, DMSO-d6) ␦: 204.2, 159.5,
137.4, 134.9, 132.5, 127.5, 125.3, 121.3, 119.8, 119.7, 119.5, 119.1, 112.4,
110.4, 109.6, 67.1, 29.7, 25.1. MS (ESI): 277 (M+H+, 100). Anal. calcd.
for C18H16N2O: C 78.24, H 5.84, N 10.14; found: C 77.95, H 6.02, N
9.87.
Straw yellow amorphous solid. IR (KBr) max: 3260, 1688, 1625,
1499 cm−1. 1H NMR (400 MHz, DMSO-d6) ␦: 10.73 (s, 1H, NH), 7.45 (s,
1H, NH), 7.33 (d, J = 8.4 Hz, 1H, Ar-H), 7.24 (s, 1H, Ar-H), 7.11 (s, 1H,
Ar-H), 7.09 (d, J = 8.4 Hz, 1H, Ar-H), 6.81 (d, J = 8.3 Hz, 1H, Ar-H), 6.76
(d, J = 8.3 Hz, 1H, Ar-H), 2.32 (s, 3H, CH3), 2.24 (s, 3H, CH3), 2.22 (s,
3H, CH3), 1.72 (s, 3H, CH3). 13C NMR (100 MHz, DMSO-d6) ␦: 204.4,
159.0, 139.2, 133.6, 133.2, 128.0, 126.8, 126.2, 124.0, 121.8, 120.0,
118.3, 112.3, 110.6, 108.7, 67.1, 25.1, 22.1, 20.6, 14.4. MS (ESI): 305
(M+H+, 100). Anal. calcd. for C22H20N2O: C 78.92, H 6.62, N 9.20;
found: C 78.57, H 6.95, N 8.90.
Published by NRC Research Press