Arbeit komplett 12.07.2003 komplett Annahmeste - ArchiMeD

10.4 Cyclisierungen 269
10.4.3.7 3-Methoxy-11H-benzo[a]carbazol-5-carbonitril (109)
9
8
10
7
10a
Summenformel: C18H12N2O
Molekulargewicht: 272.30
6b 6a
11
N
H
6
11a 11b
Einsatzmengen: 274 mg (1,0 mmol) 74
Iod
350 ml CH2Cl2
1
1'
CN
5
4a
Reaktionsbedingungen: photochemisch hν, 1h 30 min
2
4
3
1''
OCH3
Aufarbeitung: säulenchromatographisch (PE / EE = 2 / 1)
Ausbeute: 160,3 mg (589 µmol; 59%)
Schmelzpunkt: 272-274°C (Essigester/Hexan)
1 H-NMR δ [ppm]:
(300 MHz) DMSO-d6
13 C-NMR δ [ppm]:
(75 MHz) DMSO-d6
3.95 (s, 3H, CH3, 1''-H); 7.28 (dd, 3 J=7.16, 3 J=7.54, 1H,
CH, 8-H); 7.43-7.47 (m, 3H, 3xCH, 2-H, 4-H, 9-H); 7.65 (d,
3 J=7.91, 1H, CH, 10-H); 8.22 (d, 3 J=7.54, 1H, CH, 7-H);
8.55 (d, 3 J=9.04, 1H, CH, 1-H); 8.88 (s, 1H, CH, 6-H);
12.63 (s, 1H, NH)
55.2 (CH3, C-1''); 97.6 (Cq, C-5); 104.4 (CH, C-4); 111.5
(CH, C-10); 115.2 (Cq, C-6a oder C-1'); 115.4 (Cq, C-1'
oder C-6a); 118.2 (CH, C-2); 119.3 (Cq, C-11b); 119.9 (CH,
C-7); 120.2 (CH, C-8); 122.6 (Cq, C-6b); 124.5 (CH, C-1);
125.3 (CH, C-9); 128.3 (CH, C-6); 132.0 (Cq, C-4a); 138.4
(Cq, C-11a); 138.9 (Cq, C-10a); 158.6 (Cq, C-3)
EI-MS (70 eV); m/z (%) 271.6 (_, 100.00), 229.0 (51.79), 196.0 (28.60), 150.7
(40.35), 134.5 (24.18), 122.7 (28.06), 94.6 (54.00), 80.8
(78.31), 66.6 (50.22), 55.3 (99.48), 43.5 (70.36)
Elementaranalyse (%): Ber.: C: 79.40 H: 4.44 N: 10.29
Gef.: C: 77.91 H: 4.47 N: 10.00