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G.-F. Shi et al.
PAPER
IR (KBr): 3233, 1689, 1613 cm–1.
125.9, 122.6, 122.04, 121.97, 121.73, 119.0117.6, 112.0, 57.7, 34.4,
31.7, 25.2, 21.7, 21.5.
EI-MS: m/z (%) = 390 (100), 444 (M+, 45).
1H NMR (500 MHz, CDCl3): d = 11.51 (s, 1 H), 8.75 (d, J = 8.8 Hz,
1 H), 8.49 (d, J = 8.6 Hz, 1 H), 8.17 (d, J = 9.3 Hz, 1 H), 7.08 (d,
J = 7.8 Hz, 1 H), 7.80 (d, J = 8.4 Hz, 1 H), 7.72 (t, J = 8.0 Hz, 1 H),
7.66–7.69 (m, 2 H), 7.51–7.56 (m, 2 H), 5.90 (s, 1 H), 2.47–2.49 (m,
1 H), 2.38–2.41 (m, 1 H), 2.28–2.36 (m, 2 H), 1.14 (t, J = 7.4 Hz, 3
H), 1.09 (t, J = 7.5 Hz, 3 H).
13C NMR (125 MHz, CDCl3): d = 187.1, 175.9, 135.2, 134.8,
132.5, 131.8, 131.7, 130.9, 129.9, 129.5, 129.1, 128.9, 128.4, 128.1,
128.0, 123.9, 123.6, 123.1, 123.0, 122.3, 119.8, 114.4, 111.6, 63.9,
34.3, 32.4, 10.6, 9.8.
Anal. Calcd for C30H24N2O2: C, 81.06; H, 5.44; N 6.30. Found: C,
80.91; H, 5.80; N, 6.24.
10-Bromo-1-(p-bromonaphthyl)-3,3-pentamethylenebenzo[h]-
d-carbolin-2,4-dione (17h)
Yield: 61%; mp >320 °C.
IR (KBr): 3255, 1686, 1615 cm–1.
1H NMR (500 MHz, CDCl3): d = 11.08 (s, 1 H), 8.58 (br s, 1 H),
8.48 (d, J = 8.5 Hz, 1 H), 8.17–8.19 (m, 1 H), 8.05 (d, J = 7.8 Hz, 1
H), 7.80 (d, J = 8.5 Hz, 1 H), 7.72 (t, J = 7.6 Hz, 1 H), 7.65–7.67 (m,
2 H), 7.57 (t, J = 7.3 Hz, 1 H), 7.49 (d, J = 7.7 Hz, 1 H), 6.00 (s, 1
H), 2.38–2.44 (m, 3 H), 2.27–2.30 (m, 1 H), 2.04–2.07 (m, 1 H),
1.91–1.96 (m, 3 H), 1.74–1.77 (m, 1 H), 1.56–1.58 (m, 1 H).
EI-MS: m/z (%) = 560 (45), 562 (100), 564 (40), 588 (M+), 590 (60),
592 (30).
Anal. Calcd for C29H23Br2N2O2: C, 59.01; H, 3.76; N, 4.75. Found:
C, 59.16; H, 3.94; N, 4.60.
1-Naphthyl-3,3-tetramethylenebenzo[h]-d-carbolin-2,4-dione
13C NMR (125 MHz, CDCl3): d = 188.6, 175.7, 135.3, 134.5,
132.4, 132.2, 131.1, 130.7, 129.6, 129.3, 129.2, 128.8, 128.6, 128.2,
127.9, 127.8, 123.6, 123.5, 123.4, 123.2, 122.5, 118.5, 113.9, 111.5,
57.2, 33.1, 31.6, 25.2, 21.7, 21.6.
(17e)
Yield: 58%; mp >320 °C.
IR (KBr): 3240, 1686, 1616 cm–1.
1H NMR (500 MHz, DMSO-d6): d = 12.88 (s, 1 H), 8.68 (d, J = 8.2
Hz, 1 H), 8.24 (t, J = 4.9 Hz, 1 H), 8.16 (d, J = 8.2 Hz, 1 H), 7.81 (d,
J = 8.5 Hz, 1 H), 7.75–7.77 (m, 2 H), 7.70 (d, J = 7.9 Hz, 1 H), 7.61
(t, J = 7.2 Hz, 1 H), 7.56 (d, J = 7.2 Hz, 1 H), 7.48–7.51 (m, 2 H),
6.89 (d, J = 9.2 Hz, 1 H), 5.30 (d, J = 9.2 Hz, 1 H), 2.40–2.42 (m, 1
H), 2.33 (br s, 3 H), 1.89 (br s, 4 H).
13C NMR (125 MHz, CDCl3): d = 187.9, 176.7, 135.4, 135.3,
134.5, 132.8, 132.3, 131.0, 130.0, 129.1, 128.7, 128.0, 127.9,
127.35, 127.26, 126.9, 126.6, 122.9, 122.7, 122.3, 121.3, 118.7,
111.6, 63.9, 39.0, 37.8, 27.5.
EI-MS: m/z (%) = 546 (45), 548 (100), 550 (40), 600 (M+, 20), 602
(40), 604 (20).
Anal. Calcd for C30H22Br2N2O2: C, 59.82; H, 3.68; N, 4.65. Found:
C, 59.75; H, 3.47; N, 4.50.
Intermediates 2-Substituted 3-Naphthylamino-1H-benzo[g]in-
doles 24
Under N2, a solution of 15b (1 mmol) and naphthyl isonitrile 16a,b
(1 mmol) in 1,4-dioxane (25 mL) was refluxed for 10 h. To the
cooled mixture, aq 12 M HCl (2.5 mL) was added, and the mixture
was stirred at r.t. for about 20 min. After removal of the solvent, the
residue was chromatographed on a basic Al2O3 column eluting with
a mixture of PE and EtOAc (3:1) to give benzo[g]indoles 24 in 79–
83% yield.
HRMS (ESI-TOF): m/z calcd for C29H23N2O2 (M + 1): 431.1760;
found: 431.1770.
10-Bromo-1-bromonaphthyl-3,3-tetramethylenebenzo[h]-d-
carbolin-2,4-dione (17f)
Yield: 51%; mp >320 °C.
IR (KBr): 3236, 1689, 1613 cm–1.
2-(2-Ethyl-2-phenylaminocarbonyl)butanoyl-3-naphthyl-
amino-1H-benzo[g]indole (24c)
Yield: 79%; mp 230–231 °C.
1H NMR (500 MHz, DMSO-d6): d = 13.15 (s, 1 H), 8.76 (d, J = 7.8
Hz, 1 H), 8.37 (d, J = 8.6 Hz, 1 H), 8.20 (d, J = 7.9 Hz, 1 H), 7.97
(d, J = 7.8 Hz, 1 H), 7.95 (d, J = 8.5 Hz, 1 H), 7.81 (t, J = 7.5 Hz, 1
H), 7.76 (d, J = 7.9 Hz, 1 H), 7.64–7.70 (m, 4 H), 5.66 (s, 1 H),
2.37–2.42 (m, 1 H), 2.31 (br s, 3 H), 1.86–1.91 (m, 4 H).
13C NMR (125 MHz, CDCl3): d = 188.0, 176.5, 135.3, 134.6,
132.4, 132.2, 131.6, 130.7, 129.6, 129.4, 129.3, 128.8, 128.7, 128.2,
127.9, 127.8, 123.7, 123.6, 123.5, 123.2, 122.5, 118.5, 113.9, 111.7,
64.3, 38.6, 37.8, 27.44, 27.40.
IR (KBr): 3309, 1654, 1626, 1598, 1576, 1548, 1533, 1500 cm–1.
1H NMR (500 MHz, acetone-d6): d = 10.35 (s, 1 H), 9.62 (s, 1 H),
9.38 (s, 1 H), 8.29 (dd, J = 6.1, 3.2 Hz, 1 H), 8.21 (d, J = 8.1 Hz, 1
H), 8.00 (dd, J = 6.1, 3.1 Hz, 1 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.75
(d, J = 8.2 Hz, 2 H), 7.65–7.70 (m, 2 H), 7.57–7.61(m, 4 H), 7.45 (t,
J = 7.8 Hz, 1 H), 7,28–7.32 (m, 4 H), 7.24 (d, J = 8.9 Hz, 1 H), 7.09
(t, J = 9.0 Hz, 2 H), 2.47–2.52 (m, 2 H), 2.32–2.37 (m, 2 H), 0.95 (t,
J = 7.5 Hz, 6 H).
13C NMR (125 MHz, acetone-d6): d = 205.2, 188.4, 173.4, 138.5,
138.3, 134.7, 132.9, 128.8, 128.7, 128.4, 126.8, 126.4, 126.3, 126.0,
125.8, 124.5, 122.9, 121.8, 121.7, 120.9, 120.8, 120.7, 119.7, 115.7,
63.4, 23.1, 14.7, 7.5.
HRMS (FT-ICR): m/z calcd for C29H21Br2N2O2 (M + 1): 586.9964;
found: 586.9959.
1-Naphthyl-3,3-pentamethylenebenzo[h]-d-carbolin-2,4-dione
(17g)
Yield: 67%; mp >320 °C.
HRMS (ESI-TOF): m/z calcd for C35H32N3O2 (M + 1): 526.2495;
found: 526.2189.
IR (KBr): 3247, 1688, 1609 cm–1.
5-Bromo-3-(4-bromonaphthalen-1-ylamino)-2-(2-ethyl-2-phe-
nylaminocarbonyl)butanoyl-1H-benzo[g]indole (24d)
Yield: 83%; mp 167–169 °C.
IR (KBr): 3357, 3264, 1652, 1620, 1591, 1574, 1548, 1538 cm–1.
1H NMR (500 MHz, acetone-d6): d = 10.71 (s, 1 H), 9.29 (s, 1 H),
9.22 (s, 1 H), 8.35 (d, J = 8.3 Hz, 2 H), 8.28 (d, J = 8.5 Hz, 1 H),
8.24 (d, J = 8.1 Hz, 1 H), 7.66–7.79 (m, 7 H), 7.52 (s, 1 H), 7.29 (t,
J = 8.0 Hz, 2 H), 8.11 (dd, J = 8.1, 2.6 Hz, 1 H), 2.41–2.48 (m, 2 H),
2.29–2.37 (m, 2 H), 0.93 (t, J = 7.5 Hz, 6 H).
1H NMR (500 MHz, CDCl3): d = 11.44 (s, 1 H), 8.73 (d, J = 8.0 Hz,
1 H), 8.14 (d, J = 8.2 Hz, 1 H), 8.06 (d, J = 8.2 Hz, 1 H), 7.83 (d,
J = 8.4 Hz, 1 H), 7.71 (t, J = 7.1 Hz, 2 H), 7.64 (d, J = 6.9 Hz, 1 H),
7.53–7.61 (m, 3 H), 7.50 (t, J = 7.3 Hz, 1 H), 6.92 (d, J = 9.2 Hz, 1
H), 5.58 (d, J = 9.2 Hz, 1 H), 2.44–2.49 (m, 3 H), 2.32–2.35 (m, 1
H), 2.09–2.16 (m, 1 H), 1.90–2.03 (m, 3 H), 1.77–1.79 (m, 1 H),
1.54–1.61 (m, 1 H).
13C NMR (125 MHz, CDCl3): d = 189.3, 176.3, 136.7, 134.6,
134.1, 133.0, 130.9, 128.8, 128.5, 127.7, 127.4, 127.2, 126.9, 126.3,
Synthesis 2008, No. 18, 2883–2890 © Thieme Stuttgart · New York