The Journal of Organic Chemistry
Article
cm−1; MS (ESI): 357.4 (M + H)+; Anal. Calcd for C23H17ClN2: C,
77.41; H, 4.80; N, 7.85%. Found: C, 77.45; H, 4.77; N, 7.87%.
5-Bromo-2′-methyl-3-phenyl-1H,1′H-2,3′-biindole (7k). Yield:
(M + H)+; Anal. Calcd for C30H24N2O: C, 84.08; H, 5.65; N, 6.54%.
Found: C, 84.02; H, 5.69; N, 6.56%.
5-Ethoxy-2′-phenyl-3-(p-tolyl)-1H,1′H-2,3′-biindole (7r). Yield:
(344 mg) 78%; mp: 164.2−165.7 °C; Reaction time: 2.5 h; 1H
NMR (300 MHz, DMSO-d6): δ 1.13 (t, J = 4.33 Hz, 3H), 2.18 (s,
3H), 3.84 (q, 2H), 7.01−8.22 (m, 16H), 11.57 (s, 1H, NH), 11.68 (s,
1H, NH); 13C{1H} NMR (75 MHz, DMSO-d6): δ 15.3, 21.6, 56.8,
63.7, 106.9, 111.9, 114.1 (2C), 115.7 (2C), 119.9, 120.3, 122.1, 126.9,
128.0 (2C), 128.8, 128.9 (2C), 129.6 (2C), 132.5 (2C), 133.4, 135.9,
136.5, 137.7 (2C), 142.2 (2C), 150.7; IR (KBr) νmax: 3427.2, 3052.7,
1652.1, 1595.2 cm−1; MS (ESI): 443.5 (M + H)+; Anal. Calcd for
C31H26N2O: C, 84.13; H, 5.92; N, 6.33%. Found: C, 84.17; H, 5.95; N,
6.31%.
1
(328 mg) 82%; mp: 195.3−196.3 °C; Reaction time: 2 h; H NMR
(300 MHz, DMSO-d6): δ 2.08 (s, 3H), 6.59−7.89 (m, 12H), 11.10 (s,
1H, NH), 11.44 (s, 1H, NH); 13C{1H} NMR (75 MHz, DMSO-d6): δ
12.7, 102.3, 105.7, 107.0, 111.2, 112.6, 113.3, 114.7, 118.9, 119.0,
120.2, 120.7, 122.5, 128.8, 130.1, 131.8, 132.0, 132.3, 133.1, 133.2,
133.9, 134.6, 136.3; IR (KBr) νmax: 3425.4, 3067.2, 1667.0, 1592.3
cm−1; MS (ESI): 402.4 (M + H)+; Anal. Calcd for C23H17BrN2: C,
68.84; H, 4.27; N, 6.98%. Found: C, 68.87; H, 4.36; N, 6.91%.
5-Methyl-2′,3-diphenyl-1H,1′H-2,3′-biindole (7l). Yield: (318 mg)
80%; mp: 161.6−162.4 °C; Reaction time: 2.5 h; 1H NMR (300 MHz,
DMSO-d6): δ 2.19 (s, 3H), 6.53−7.93 (m, 17H), 11.55 (s, 1H, NH),
11.99 (s, 1H, NH); 13C{1H} NMR (75 MHz, DMSO-d6): δ 21.6,
106.3, 107.0, 111.6, 111.8, 119.2, 119.6, 119.7, 122.3, 123.9, 126.6,
126.6, 127.2, 127.3 (2C), 128.0, 128.8 (2C), 129.8, 130.0, 130.3, 133.4,
133.5, 135.0, 135.1, 135.3, 136.9; IR (KBr) νmax: 3419.2, 3065.5,
1669.2, 1595.4 cm−1; MS (ESI): 399.2 (M + H)+; Anal. Calcd for
C29H22N2: C, 87.41; H, 5.56; N, 7.03%. Found: C, 87.48; H, 5.52; N,
7.06%.
5-Ethoxy-3-(4-nitrophenyl)-2′-phenyl-1H,1′H-2,3′-biindole (7s).
1
Yield: (373 mg) 79%; mp: 179.3−180.2 °C; Reaction time: 2 h; H
NMR (300 MHz, DMSO-d6): δ 1.10 (t, J = 5.26 Hz, 3H), 3.83 (q,
2H), 7.05−8.32 (m, 16H), 11.59 (s, 1H, NH), 11.69 (s, 1H, NH);
13C{1H} NMR (75 MHz, DMSO-d6): δ 15.4, 56.8, 63.7, 106.8, 111.9,
114.2 (2C), 115.7 (2C), 119.9, 120.3, 122.2, 126.9, 128.1 (2C), 128.8,
128.9 (2C), 129.7 (2C), 132.5 (2C), 133.4, 135.8, 136.6, 137.6 (2C),
142.2 (2C), 150.7; IR (KBr) νmax: 3436.2, 3059.5, 1658.2, 1597.5
cm−1; MS (ESI): 474.1 (M + H)+; Anal. Calcd for C30H23N3O3: C,
76.09; H, 4.90; N, 8.87%. Found: C, 76.15; H, 4.79; N, 8.90%.
3-(4-Chlorophenyl)-5-ethoxy-2′-phenyl-1H,1′H-2,3′-biindole (7t).
5-Methyl-2′-phenyl-3-(p-tolyl)-1H,1′H-2,3′-biindole (7m). Yield:
(325 mg) 79%; mp: 161.7−162.9 °C; Reaction time: 2.5 h; 1H
NMR (300 MHz, DMSO-d6): δ 2.18 (s, 6H), 6.18−7.20 (m, 16H),
11.38 (s, 1H, NH), 11.56 (s, 1H, NH); 13C{1H} NMR (75 MHz,
DMSO-d6): δ 21.6 (2C), 106.3, 107.0, 119.5, 119.7, 122.2, 123.9,
126.6, 126.7, 127.2, 127.3, 128.0 (2C), 128.8 (2C), 128.9, 130.1, 130.3,
1
Yield: (364 mg) 79%; mp: 180.1−182.3 °C; Reaction time: 2.5 h; H
NMR (300 MHz, DMSO-d6): δ 1.11 (t, J = 6.06 Hz, 3H), 3.83 (q,
2H), 7.10−8.35 (m, 16H), 11.55 (s, 1H, NH), 11.68 (s, 1H, NH);
13C{1H} NMR (75 MHz, DMSO-d6): δ 15.5, 56.6, 63.8, 106.6, 111.8,
114.2 (2C), 115.8 (2C), 120.0, 120.3, 122.2, 126.9, 128.1 (2C), 128.8,
128.9 (2C), 129.6 (2C), 132.4 (2C), 133.5, 135.8, 136.6, 137.7 (2C),
142.2 (2C), 150.7; IR (KBr) νmax: 3437.5, 3077.3, 1688.2, 1589.2
cm−1; MS (ESI): 463.7 (M + H)+; Anal. Calcd for C30H23ClN2O: C,
77.83; H, 5.01; N, 6.05%. Found: C, 77.80; H, 5.05; N, 6.08%.
5-Methyl-3-phenyl-1H,1′H-2,3′-biindole (7u). Yield: (209 mg)
65%; mp: 205.5−207.3 °C; Reaction time: 2.5 h; 1H NMR (300
MHz, DMSO-d6): δ 2.32 (s, 3H), 6.80−7.57 (m, 13H), 11.20 (s, 1H,
NH), 11.34 (s, 1H, NH); 13C{1H} NMR (75 MHz, DMSO-d6): δ
21.6, 106.4, 109.0, 111.3, 111.9, 118.8, 119.2, 119.9, 121.3, 123.7,
124.5, 127.1, 127.4 (2C), 127.8, 128.6 (2C), 130.2, 133.6, 134.3, 134.9,
136.1, 136.7; IR (KBr) νmax: 3423.3, 3073.2, 1668.4, 1590.2 cm−1; MS
(ESI): 323.1 (M + H)+; Anal. Calcd for C23H18N2: C, 85.68; H, 5.63;
N, 8.69%. Found: C, 85.74; H, 5.56; N, 8.78%.
133.4 (2C), 133.5, 135.0, 135.1, 135.3, 136.9(2C) ; IR (KBr) νmax
:
3429.3, 3059.2, 1655.4, 1595.5 cm−1; MS (ESI): 413.2 (M + H)+;
Anal. Calcd for C30H24N2: C, 87.35; H, 5.86; N, 6.79%. Found: C,
87.29; H, 5.92; N, 6.76%.
3-(4-Methoxyphenyl)-5-methyl-2′-phenyl-1H,1′H-2,3′-biindole
(7n). Yield: (333 mg) 78%; mp: 165.3−166.2 °C; Reaction time: 2.5 h;
1H NMR (300 MHz, DMSO-d6): δ 2.05 (s, 3H), 3.72 (s, 3H), 6.80−
7.89 (m, 16H), 11.32 (s, 1H, NH), 11.57 (s, 1H, NH); 13C{1H} NMR
(75 MHz, DMSO-d6): δ 21.6, 55.8, 106.9, 111.4, 119.7, 122.3, 123.9,
126.6 (2C), 126.7(2C), 127.3, 127.3 (2C), 127.9 (2C), 128.8 (2C),
128.9, 130.1 (2C), 130.2, 133.4 (2C), 133.5, 135.0, 135.2, 135.2, 136.9,
158.6; IR (KBr) νmax: 3427.9, 3058.5, 1679.1, 1595.7 cm−1; MS (ESI):
429.2 (M + H)+; Anal. Calcd for C30H24N2O: C, 84.08; H, 5.65; N,
6.54%. Found: C, 84.11; H, 5.67; N, 6.51%.
5-Methyl-3-(4-nitrophenyl)-2′-phenyl-1H,1′H-2,3′-biindole (7o).
Yield: (354 mg) 80%; mp: 170.1−172.3 °C; Reaction time: 2.5 h;
1H NMR (300 MHz, DMSO-d6): δ 2.20 (s, 3H), 6.41−8.38 (m, 16H),
3-Phenyl-1H,1′H-2,3′-biindole (7v). Yield: (206 mg) 67%; mp:
1
187.3−189.1 °C; Reaction time: 2.5 h; H NMR (300 MHz, DMSO-
d6): 7.16−7.24 (m, 2H), 7.25−8.03(m, 12H), 11.01 (s, 1H, NH),
11.29 (s, 1H, NH); 13C{1H} NMR (75 MHz, DMSO-d6): δ 105.8,
108.8, 111.0, 114.6, 115.3 (2C), 118.5, 119.3 (2C), 120.7, 125.6, 126.9,
129.0 (2C), 130.2 (2C), 134.9, 135.0, 135.5, 138.1, 141.7, 142.9; IR
(KBr) νmax: 3419.6, 3080.4, 1666.7, 1594.2 cm−1; MS (ESI): 309.1 (M
+ H)+; Anal. Calcd for C22H16N2: C, 85.69; H, 5.23; N, 9.08%. Found:
C, 85.62; H, 5.58; N, 9.13%.
11.68 (s, 1H, NH), 11.75 (s, 1H, NH); 13C{1H} NMR (75 MHz,
DMSO-d6): δ 21.6, 106.0, 109.9, 112.0, 119.5, 119.8, 122.5, 124.0,
124.1, 125.5 (2C), 126.9, 127.0, 127.5, 128.7 (2C), 128.8, 129.1, 129.4
(2C), 129.6, 129.9, 132.6, 133.1, 135.3, 136.1, 137.0, 140.0, 145.7; IR
(KBr) νmax: 3439.4, 3060.5, 1659.2, 1595.7 cm−1; MS (ESI): 444.2 (M
+ H)+; Anal. Calcd for C29H21N3O2: C, 78.54; H, 4.77; N, 9.47%.
Found: C, 78.50; H, 4.80; N, 9.49%.
Experimental Procedure for the Synthesis of Intermediate
[B]. Equimolar amounts of toludine 1 (107 mg, 1 mmol),
phenylglyoxal monohydrate 2 (152 mg, 1 mmol), and 2-methylindole
6 (131 mg, 1 mmol) were taken in a round-bottom flask containing
acetonitrile (5 mL). Then, 5 mol % FeCl3 was added to the reaction
mixture, and the resulting mixture was stirred at room temperature for
1 h. The solid compound obtained was filtered and further purified by
column chromatography using hexane and ethyl acetate (8:2 ratio) as
eluent, which gave the compound [B] in (254 mg) 72% yield. The
structure of the compound was determined from the spectroscopic
data.
3-(4-Chlorophenyl)-5-methyl-2′-phenyl-1H,1′H-2,3′-biindole
(7p). Yield: (345 mg) 80%; mp: 172.2−173.1 °C; Reaction time: 2.5 h;
1H NMR (300 MHz, DMSO-d6): δ 2.18 (s, 3H), 6.49−8.39 (m, 16H),
11.66 (s, 1H, NH), 11.74 (s, 1H, NH); 13C{1H} NMR (75 MHz,
DMSO-d6): δ 21.5, 105.9, 109.9, 112.0, 119.5, 119.9, 122.5, 123.9,
124.1, 125.6 (2C), 126.8, 127.0, 127.6, 128.7 (2C), 128.8, 129.0, 129.4
(2C), 129.6, 129.9, 132.6, 133.2, 135.4, 136.1, 137.1, 139.9, 145.7; IR
(KBr) νmax: 3429.2, 3058.5, 1669.3, 1595.5 cm−1; MS (ESI): 433.2 (M
+ H)+; Anal. Calcd for C29H21ClN2: C, 80.45; H, 4.89; N, 6.47%.
Found: C, 80.50; H, 4.82; N, 6.50%.
Intermediate [B]. Yield: (254 mg) 72%; 1H NMR (300 MHz,
DMSO-d6): δ 2.28 (s, 3H), 2.34 (s, 3H), 5.68 (s, 1H), 6.39 (s, NH),
6.65−7.95 (m, 13H), 11.00 (s, NH); 13C{1H} NMR (75 MHz,
DMSO-d6): δ 15.2, 21.3, 65.7, 106.9, 111.9, 114.1, 115.7, 119.8, 120.3,
122.1, 126.9, 128.0, 128.8, 128.9 (2C), 129.5, 132.4, 133.4, 135.9,
136.5, 137.5, 142.1, 150.6, 197.2.
5-Ethoxy-2′,3-diphenyl-1H,1′H-2,3′-biindole (7q). Yield: (338 mg)
79%; mp: 163.3−164.9 °C; Reaction time: 2.5 h; 1H NMR (300 MHz,
DMSO-d6): δ 1.11 (t, J = 5.80 Hz, 3H), 3.83 (q, 2H), 7.00−8.32 (m,
17H), 11.58 (s, 1H, NH), 11.64 (s, 1H, NH); 13C{1H} NMR (75
MHz, DMSO-d6): δ 15.3, 56.8, 63.7, 107.0, 111.9, 114.1 (2C), 115.7
(2C), 119.9, 120.3, 122.1, 127.0, 128.0 (2C), 128.8, 128.9 (2C), 129.5
(2C), 132.4 (2C), 133.4, 135.9, 136.5, 137.6 (2C), 142.1 (2C), 150.7;
IR (KBr) νmax: 3429.7, 3063.5, 1654.5, 1590.4 cm−1; MS (ESI): 429.2
Synthesis of 7a from [B]. The intermediate [B] (354 mg, 1
mmol) in acetonitrile (5 mL) was stirred at 60 °C in the presence of
H
J. Org. Chem. XXXX, XXX, XXX−XXX