A Versatile Synthesis of Annulated Carbazole Analogs
3f: The annulation of bromide 1c (0.2 g, 0.38 mmol) with 1-methyl-
naphthalene (0.06 mL, 0.42 mmol) by using ZnBr2 (0.17 g,
0.75 mmol) in dry 1,2-DCE (8 mL) following the same procedure
as that of 3c afforded compound 3f (0.09 g, 56%) as a colorless
solid. M.p. 206 °C. 1H NMR (300 MHz, CDCl3): δ = 9.56 (s, 1 H),
8.89 (d, J = 8.1 Hz, 1 H), 8.34 (d, J = 8.4 Hz, 1 H), 8.10 (s, 1 H),
1 H), 8.14 (s, 1 H), 7.92 (d, J = 7.2 Hz, 1 H), 7.80 (d, J = 7.2 Hz,
2 H), 7.50–7.28 (m, 7 H), 4.06 (s, 3 H), 4.01 (s, 3 H) ppm. 13C
NMR (75.4 MHz, CDCl3): δ = 150.0, 149.3, 139.5, 137.7, 136.4,
133.7, 129.1, 129.0, 127.7, 126.8, 126.5, 125.2, 124.2, 120.1, 116.8,
115.4, 111.0, 106.7, 106.0, 56.0, 55.9 ppm. MS (EI): m/z (%) = 417
(59) [M]+. C24H19NO4S (417.10): calcd. C 69.05, H 4.59, N 3.36, S
8.01 (d, J = 7.8 Hz, 1 H), 7.90 (d, J = 7.8 Hz, 1 H), 7.80 (d, J = 7.68; found C 69.25, H 4.82, N 3.65, S 7.46.
7.5 Hz, 2 H), 7.74–7.46 (m, 4 H), 7.36–7.15 (m, 4 H), 2.67 (s, 3 H)
3k: The annulation of bromide 1d (0.2 g, 0.36 mmol) with veratrole
ppm. 13C NMR (75.4 MHz, CDCl3): δ = 139.7, 137.6, 137.4, 133.8,
132.1, 131.9, 130.6, 129.5, 129.1, 129.0, 128.0, 126.9, 126.6, 126.5,
124.8, 124.2, 123.5, 120.5, 118.3, 115.5, 108.0, 20.0 ppm. MS (EI):
m/z (%) = 421 (65) [M]+. C27H19NO2S (421.11): calcd. C 76.93, H
4.54, N 3.32, S 7.61; found C 76.66, H 4.62, N 3.57, S 7.93.
(0.06 mL, 0.43 mmol) by using ZnBr2 (0.16 g, 0.71 mmol) in dry
1,2-DCE (8 mL) following the same procedure as that of 3c af-
forded compound 3k (0.07 g, 44%) as a colorless solid. M.p. 240–
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242 °C. H NMR (300 MHz, CDCl3): δ = 8.56 (s, 1 H), 8.19 (d, J
= 9.0 Hz, 1 H), 8.09 (s, 1 H), 7.75 (d, J = 8.1 Hz, 2 H), 7.40–7.20
(m, 6 H), 7.05 (dd, J = 1.8, 9.0 Hz, 1 H), 4.07 (s, 3 H), 4.02 (s, 3
H), 3.90 (s, 3 H) ppm. 13C NMR (75.4 MHz, CDCl3): δ = 157.1,
150.0, 149.3, 137.5, 137.0, 133.7, 133.5, 129.2, 128.9, 128.0, 126.5,
125.4, 116.8, 116.5, 115.0, 111.4, 106.7, 106.1, 104.0, 55.9 (2 C),
55.8 ppm. MS (EI): m/z (%) = 447 (24) [M]+. C25H21NO5S (447.11):
calcd. C 67.10, H 4.73, N 3.13, S 7.17; found C 67.30, H 4.61, N
3.32, S 7.43.
3g: The annulation of bromide 1d (0.3 g, 0.54 mmol) with 1-methyl-
naphthalene (0.09 mL, 0.63 mmol) by using anhydrous ZnBr2
(0.25 g, 1.11 mmol) in dry 1,2-DCE (10 mL) following the same
procedure as that of 3c afforded compound 3g (0.11 g, 44%) as a
colorless solid. M.p. 276–278 °C. 1H NMR (300 MHz, CDCl3): δ
= 9.60 (s, 1 H), 8.95 (d, J = 7.8 Hz, 1 H), 8.27 (d, J = 9.0 Hz, 1
H), 8.19 (s, 1 H), 8.09 (d, J = 7.8 Hz, 1 H), 7.80–7.65 (m, 6 H),
7.46 (d, J = 7.2 Hz, 1 H), 7.37 (t, J = 7.5 Hz, 1 H), 7.26–7.19 (m,
1 H), 7.11 (dd, J = 2.7, 9.0 Hz, 1 H), 3.93 (s, 3 H), 2.75 (s, 3 H)
ppm. 13C NMR (75.4 MHz, CDCl3): δ = 157.2, 138.1, 137.4, 134.0,
133.6, 132.2, 132.0, 130.1, 129.1, 128.9, 127.0, 126.7, 126.6, 126.5,
124.8, 123.5, 118.3, 116.7, 115.7, 108.6, 104.0, 55.8, 20.0 ppm. MS
(EI): m/z (%) = 451 (15) [M]+. C28H21NO3S (451.12): calcd. C
74.48, H 4.69, N 3.10, S 7.10; found C 74.69, H 4.52, N 3.28, S
7.34.
3l: The annulation of bromide 1c (0.3 g, 0.57 mmol) with m-xylene
(0.08 mL, 0.65 mmol) by using ZnBr2 (0.26 g, 1.15 mmol) in dry
1,2-DCE (10 mL) following the same procedure as that of 3c af-
forded compound 3l (0.12 g, 55%) as a colorless solid. M.p. 208 °C.
1H NMR (300 MHz, CDCl3): δ = 8.85 (s, 1 H), 8.38 (d, J = 8.1 Hz,
1 H), 8.20 (s, 1 H), 7.98 (d, J = 7.5 Hz, 1 H), 7.85–7.82 (m, 2 H),
7.58–7.52 (m, 2 H), 7.39 (t, J = 7.3 Hz, 2 H), 7.29–7.24 (m, 3 H),
2.85 (s, 3 H), 2.52 (s, 3 H) ppm. 13C NMR (75.4 MHz, CDCl3): δ
= 140.1, 137.6, 136.8, 134.4, 134.3, 133.7, 131.1, 130.6, 129.2, 128.9,
128.2, 126.5, 126.4, 125.2, 124.2, 120.6, 118.2, 115.4, 108.7, 21.5,
19.9 ppm. MS (EI): m/z (%) = 385 (38) [M]+. C24H19NO2S (385.11):
calcd. C 74.78, H 4.97, N 3.63, S 8.32; found C 74.48, H 5.09, N
3.90, S 8.60.
3h: The annulation of bromide 1c (0.2 g, 0.38 mmol) with 2-meth-
oxynaphthalene (0.07 g, 0.44 mmol) by using ZnBr2 (0.17 g,
0.75 mmol) in dry 1,2-DCE (8 mL) following the same procedure
as that of 3c afforded compound 3h (0.08 g, 47%) as a colorless
1
solid. M.p. 172–174 °C. H NMR (300 MHz, CDCl3): δ = 9.03 (s,
1 H), 8.74 (s, 1 H), 8.65 (d, J = 8.7 Hz, 1 H), 8.35 (d, J = 8.4 Hz,
1 H), 8.09 (d, J = 7.8 Hz, 1 H), 7.90 (d, J = 9.0 Hz, 1 H), 7.84 (d,
J = 7.8 Hz, 2 H), 7.69 (d, J = 9.0 Hz, 1 H), 7.54 (t, J = 7.5 Hz, 2
H), 7.45–7.38 (m, 3 H), 7.32–7.24 (m, 2 H), 3.97 (s, 3 H) ppm. 13C
NMR (75.4 MHz, CDCl3): δ = 158.4, 139.7, 137.7, 136.9, 133.8,
133.1, 131.0, 129.0, 128.1 (2 C), 126.9, 126.7, 126.6, 126.5, 124.6,
124.3, 124.1, 120.4, 117.1, 115.4, 113.5, 113.1, 108.9, 55.5 ppm. MS
(EI): m/z (%) = 437 (43) [M]+. C27H19NO3S (437.11): calcd. C
74.12, H 4.38, N 3.20, S 7.33; found C 74.34, H 4.18, N 3.43, S
7.12.
3m: The annulation of bromide 1d (0.2 g, 0.36 mmol) with m-xylene
(0.06 mL, 0.47 mmol) by using ZnBr2 (0.16 g, 0.71 mmol) in dry
1,2-DCE (8 mL) following the same procedure as that of 3c af-
forded compound 3m (0.08 g, 53%) as a colorless solid. M.p. 186–
1
188 °C. H NMR (300 MHz, CDCl3): δ = 8.79 (s, 1 H), 8.23 (d, J
= 9.0 Hz, 1 H), 8.15 (s, 1 H), 7.73 (d, J = 7.5 Hz, 2 H), 7.57 (s, 1
H), 7.43–7.34 (m, 2 H), 7.25–7.20 (m, 3 H), 7.08 (dd, J = 2.7,
9.0 Hz, 1 H), 3.91 (s, 3 H), 2.82 (s, 3 H), 2.50 (s, 3 H) ppm. 13C
NMR (75.4 MHz, CDCl3): δ = 157.1, 137.5, 137.4, 134.5, 134.4,
134.3, 133.6, 131.1, 130.7, 129.3, 128.8, 127.8, 126.7, 126.5, 125.2,
118.2, 116.6, 115.7, 109.2, 104.2, 55.8, 21.6, 19.9 ppm. MS (EI):
m/z (%) = 415 (77) [M]+. C25H21NO3S (415.12): calcd. C 72.27, H
5.09, N 3.37, S 7.72; found C 72.03, H 5.30, N 3.53, S 7.53.
3i: The annulation of bromide 1c (0.31 g, 0.59 mmol) with o-xylene
(0.09 mL, 0.75 mmol) by using anhydrous ZnBr2 (0.27 g,
1.19 mmol) in dry 1,2-DCE (10 mL) following the same procedure
as that of 3c afforded compound 3i (0.13 g, 56%) as a colorless
solid. M.p. 204 °C. 1H NMR (300 MHz, CDCl3): δ = 8.65 (s, 1 H),
8.30 (d, J = 8.1 Hz, 1 H), 8.11 (s, 1 H), 7.9 (d, J = 7.5 Hz, 1 H),
7.78 (d, J = 8.7 Hz, 3 H), 7.63 (s, 1 H), 7.47 (t, J = 7.2 Hz, 1 H),
7.37–7.30 (m, 2 H), 7.20 (t, J = 9 Hz, 2 H), 2.63 (s, 3 H), 2.48 (s,
3 H) ppm. 13C NMR (75.4 MHz, CDCl3): δ = 139.9, 137.7, 136.8,
136.0, 135.0, 133.6, 132.0, 129.7, 128.9, 128.0, 127.8, 127.3, 126.8,
126.5, 126.1, 124.2, 120.4, 117.3, 115.4, 111.3, 20.3, 20.2 ppm. MS
(EI): m/z (%) = 385 (81) [M]+. C24H19NO2S (385.11): calcd. C
74.78, H 4.97, N 3.63, S 8.32; found C 74.88, H 4.76, N 3.87, S
8.50.
3n: The annulation of bromide 1c (0.3 g, 0.57 mmol) with p-xylene
(0.08 mL, 0.65 mmol) by using ZnBr2 (0.26 g, 1.15 mmol) in dry
1,2-DCE (10 mL) following the same procedure as that of 3c af-
forded compound 3n (0.11 g, 50%) as a colorless solid. M.p.
1
182 °C. H NMR (300 MHz, CDCl3): δ = 8.90 (s, 1 H), 8.48 (s, 1
H), 8.39 (d, J = 8.4 Hz, 1 H), 8.07 (d, J = 7.8 Hz, 1 H), 7.85 (d, J
= 7.5 Hz, 2 H), 7.58–7.53 (m, 1 H), 7.45–7.39 (m, 2 H), 7.34–7.32
(m, 4 H), 2.86 (s, 3 H), 2.78 (s, 3 H) ppm. 13C NMR (75.4 MHz,
CDCl3): δ = 140.1, 137.6, 137.0, 133.8, 132.7, 132.5, 132.4, 130.0,
129.0, 128.2, 126.7, 126.5, 126.0, 125.5, 124.3, 120.6, 115.4 (2 C),
109.4, 20.0, 19.7 ppm. MS (EI): m/z (%) = 385 (47) [M]+.
C24H19NO2S (385.11): calcd. C 74.78, H 4.97, N 3.63, S 8.32; found
C 74.58, H 4.85, N 3.92, S 8.59.
3j: The annulation of bromide 1c (0.41 g, 0.78 mmol) with veratrole
(0.12 mL, 0.94 mmol) by using ZnBr2 (0.35 g, 1.55 mmol) in dry
1,2-DCE (12 mL) following the same procedure as that of 3c af-
forded compound 3j (0.19 g, 57%) as a colorless solid. M.p. 210 °C.
1H NMR (300 MHz, CDCl3): δ = 8.58 (s, 1 H), 8.29 (d, J = 8.1 Hz,
3o: The annulation of bromide 1c (0.31 g, 0.59 mmol) with 1,4-
dimethoxybenzene (0.10 g, 0.72 mmol) by using ZnBr2 (0.27 g,
1.19 mmol) in dry 1,2-DCE (10 mL) following the same procedure
Eur. J. Org. Chem. 2009, 531–546
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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