D
Synlett
U. Kober, H.-J. Knölker
Letter
(
c) Hesse, R.; Gruner, K. K.; Kataeva, O.; Schmidt, A. W.; Knölker,
1374, 1354, 1304, 1225, 1183, 1152, 1077, 1020, 903, 805, 748,
–1 1
H.-J. Chem. Eur. J. 2013, 19, 14098. (d) Kumar, V. P.; Gruner, K.
K.; Kataeva, O.; Knölker, H.-J. Angew. Chem. Int. Ed. 2013, 52,
1
695 cm . H NMR (500 MHz, CDCl ): δ = 2.68 (s, 3 H), 6.26 (br s,
3
1 H), 6.85 (t, J = 7.4 Hz, 1 H), 6.90 (d, J = 8.3 Hz, 2 H), 7.18–7.23
(m, 3 H), 7.41–7.45 (m, 4 H), 7.86 (d, J = 8.0 Hz, 1 H), 8.19 (br s, 1
1073. (e) Hesse, R.; Jäger, A.; Knölker, H.-J. Org. Biomol. Chem.
014, 12, 3866. (f) Hesse, R.; Krahl, M. P.; Jäger, A.; Kataeva, O.;
13
2
H). C NMR and DEPT (125 MHz, CDCl ): δ = 31.68 (CH ),
3
3
Schmidt, A. W.; Knölker, H.-J. Eur. J. Org. Chem. 2014, 4014.
g) Gassner, C.; Hesse, R.; Schmidt, A. W.; Knölker, H.-J. Org.
Biomol. Chem. 2014, 12, 6490.
110.95 (CH), 113.05 (CH), 115.90 (2 CH), 119.37 (C), 119.78
(CH), 119.80 (CH), 121.55 (C), 122.19 (CH), 122.35 (CH), 126.30
(CH), 129.33 (2 CH), 129.49 (C), 131.49 (C), 136.22 (C), 140.18
(C), 145.58 (C), 205.90 (C=O). MS (EI): m/z = 300 (100), 285 (67),
284 (18), 257 (48), 256 (45), 255 (30).
(
(
(
(
15) (a) Knölker, H.-J.; Reddy, K. R. Tetrahedron Lett. 1998, 39, 4007.
(
b) Knölker, H.-J.; Reddy, K. R. Tetrahedron 2000, 56, 4733.
16) Zhuang, J.; Wang, C.; Xie, F.; Zhang, W. Tetrahedron 2009, 65,
797.
17) (a) Charles, M. D.; Schulz, P.; Buchwald, S. L. Org. Lett. 2005, 7,
(22) Gensch, T.; Rönnefahrt, M.; Czerwonka, R.; Jäger, A.; Kataeva, O.;
Bauer, I.; Knölker, H.-J. Chem. Eur. J. 2012, 18, 770.
(23) Liebermann, H. Ann. Chem. 1914, 404, 272.
9
3
965. (b) Surry, D. S.; Buchwald, S. L. Angew. Chem. Int. Ed. 2008,
(24) (a) Knölker, H.-J.; O’Sullivan, N. Tetrahedron 1994, 50, 10893.
(b) Knölker, H.-J.; Fröhner, W.; Reddy, K. R. Synthesis 2002, 557.
(c) Schmidt, M.; Knölker, H.-J. Synlett 2009, 2421.
47, 6338.
(
18) 2′,5′-Bis(phenylamino)acetophenone (5)
Orange oil. IR (ATR): ν = 3380, 3276, 3034, 2921, 2851, 1641,
(25) Åkermark, B.; Eberson, L.; Jonsson, E.; Pettersson, E. J. Org. Chem.
1975, 40, 1365.
(26) (a) Börger, C.; Knölker, H.-J. Synlett 2008, 1698. (b) Börger, C.;
Knölker, H.-J. Tetrahedron 2012, 68, 6727.
1
1
619, 1595, 1575, 1512, 1492, 1465, 1420, 1398, 1360, 1306,
245, 1204, 1076, 1025, 994, 957, 933, 874, 814, 743, 692, 664
–1 1
cm . H NMR (500 MHz, DMSO-d ): δ = 2.57 (s, 3 H), 6.74 (t, J =
6
7
.3 Hz, 1 H), 6.94–7.03 (m, 3 H), 7.17–7.20 (m, 4 H), 7.25–7.33
(27) Wang, W.; Li, T.; Attardo, G. J. Org. Chem. 1997, 62, 6598.
(28) Malasseziazole C (12-Formyl-5,11-dihydroindolo[3,2-b]car-
bazole-6-carboxylic Acid) (3)
(
m, 4 H), 7.62 (d, J = 1.9 Hz, 1 H), 7.98 (br s, 1 H), 9.88 (br s, 1 H).
1
3
C NMR and DEPT (125 MHz, DMSO-d ): δ = 28.53 (CH ),
6
3
1
14.91 (2 CH), 116.81 (CH), 118.57 (CH), 120.01 (2 CH), 121.68
Brownish solid; mp >300 °C (decomp.). UV (MeOH): λ = 213,
247, 272 (sh), 307 (sh), 391, 465 nm. Fluorescence (MeOH): λex
= 307 nm, λem = 455 nm. IR (ATR): ν = 3448, 3055, 2922, 2852,
1712, 1611, 1585, 1512, 1458, 1392, 1347, 1321, 1299, 1263,
1205, 1158, 1126, 1077, 1022, 954, 895, 839, 804, 741, 698, 653
(C), 122.00 (CH), 122.10 (CH), 126.81 (CH), 129.26 (2 CH),
1
2
29.49 (2 CH), 133.98 (C), 139.91 (C), 141.46 (C), 144.89 (C),
01.24 (C=O). MS (EI): m/z = 302 (100), 287 (12), 285 (10), 256
(10), 195 (47), 183 (16), 167 (54), 166 (22), 154 (14), 128 (13),
–1 1
77 (18), 51 (9). Anal. Calcd (%) for C20H18N O: C, 79.44; H, 6.00;
cm . H NMR (500 MHz, DMSO-d ): δ = 7.22 (m, 2 H), 7.48 (t, J =
2
6
N, 9.26. Found: C, 79.42; H, 5.99; N, 9.16.
7.6 Hz, 1 H), 7.52 (t, J = 7.7 Hz, 1 H), 7.79 (d, J = 8.2 Hz, 1 H), 7.82
(d, J = 8.1 Hz, 1 H), 8.58 (d, J = 8.2 Hz, 1 H), 8.61 (d, J = 8.1 Hz, 1
(
19) (a) Forke, R.; Krahl, M. P.; Däbritz, F.; Jäger, A.; Knölker, H.-J.
Synlett 2008, 1870. (b) Liégault, B.; Lee, D.; Huestis, M. P.;
Stuart, D. R.; Fagnou, K. J. Org. Chem. 2008, 73, 5022.
H), 11.41 (s, 1 H), 11.44 (s, 1 H), 11.96 (s, 1 H), 13.72 (br s, 1 H).
1
H NMR (600 MHz, CD OD): δ = 7.11–7.13 (m, 1 H), 7.19–7.21
3
(
2
2
c) Fuchsenberger, M.; Forke, R.; Knölker, H.-J. Synlett 2011,
056. (d) Huet, L.; Forke, R.; Jäger, A.; Knölker, H.-J. Synlett 2012,
3, 1230.
(m, 1 H), 7.40–7.45 (m, 2 H), 7.60 (d, J = 8.0 Hz, 1 H), 7.61 (d, J =
7.9 Hz, 1 H), 8.33 (d, J = 8.0 Hz, 1 H), 8.91 (d, J = 8.2 Hz, 1 H),
13
11.50 (br s, 1 H). C NMR and DEPT (125 MHz, DMSO-d ): δ =
6
(
20) 6-Acetyl-5,11-dihydro-indolo[3,2-b]carbazole (10)
112.60 (CH), 112.72 (CH), 114.57 (C), 114.93 (C), 119.56 (CH),
119.77 (CH), 120.36 (C), 120.62 (C), 121.15 (C), 123.31 (C),
124.42 (CH), 125.09 (CH), 127.18 (CH), 127.51 (CH), 134.33 (C),
135.39 (C), 142.38 (C), 142.70 (C), 168.57 (C=O), 191.11 (CHO).
Yellow solid; mp 244 °C. UV (MeOH): λ = 213 (sh), 223, 254,
306, 338 (sh), 357, 438 nm. Fluorescence (MeOH): λex = 223 nm,
λem = 507 nm. IR (ATR): ν = 3456, 3400, 3051, 2920, 2851, 1640,
+
1
1
6
605, 1558, 1512, 1457, 1418, 1353, 1320, 1292, 1270, 1221,
ESI-MS (+25 V): m/z = 329.1 [M + H] .
186, 1168, 1144, 1109, 1010, 988, 961, 934, 866, 739, 692, 641,
(29) 5,11-Dihydroindolo[3,2-b]carbazole-6,12-dicarboxylic Acid
(17)
–1 1
21 cm . H NMR (600 MHz, CDCl ): δ = 2.96 (s, 3 H), 7.23–7.28
3
(
m, 2 H), 7.46–7.49 (m, 3 H), 7.51–7.52 (m, 1 H), 8.10 (d, J = 7.8
Red solid; mp >294 °C (decomp.). UV (MeOH): λ = 211, 275 (sh),
294, 366 nm. Fluorescence (MeOH): λex = 294 nm, λem = 515 nm.
IR (ATR): ν = 3448, 3413, 2920, 2850, 2577, 1642, 1610, 1570,
1543, 1501, 1473, 1457, 1429, 1314, 1297, 1229, 1207, 1151,
Hz, 1 H), 8.17 (d, J = 8.1 Hz, 1 H), 8.22 (s, 1 H), 8.28 (br s, 1 H),
9
.72 (br s, 1 H). 1 C NMR and DEPT (150 MHz, CDCl ): δ = 30.93
3
3
(
(
(
(
(
CH ), 106.42 (CH), 110.95 (CH), 111.00 (CH), 115.07 (C), 119.26
3
–1
1
CH), 119.46 (CH), 120.26 (C), 120.31 (CH), 121.90 (C), 122.37
C), 124.08 (CH), 124.25 (C), 126.40 (CH), 126.73 (CH), 135.09
C), 135.29 (C), 141.15 (2 C), 202.85 (C=O). MS (EI): m/z = 298
100), 283 (30), 255 (64), 254 (10), 253 (11), 227 (11).
1112, 1021, 891, 857, 793, 763, 746, 699, 624 cm . H NMR
(500 MHz, DMSO-d ): δ = 7.16 (m, 2 H), 7.45 (m, 2 H), 7.75 (d, J =
6
8.1 Hz, 2 H), 8.67 (d, J = 8.2 Hz, 2 H), 11.25 (s, 2 H), 13.95 (br s, 2
13
H). C NMR and DEPT (125 MHz, DMSO-d ): δ = 110.44 (2 C),
6
(
21) 4-Acetyl-3-(phenylamino)carbazole (11)
111.63 (2 CH), 118.31 (2 CH), 120.35 (2 C), 120.63 (2 C), 124.28
(2 CH), 126.57 (2 CH), 134.72 (2 C), 141.81 (2 C), 168.47 (2 C=O).
ESI-MS (+10 V): m/z = 345.2 [M + H] .
Yellow solid; mp 153 °C. UV (MeOH): λ = 204, 242, 306, 348
+
(sh), 452 nm. Fluorescence (MeOH): λex = 306 nm, λem = 411 nm.
IR (ATR): ν = 3404, 2924, 2853, 1737, 1689, 1601, 1496, 1444,
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Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, A–D