Arbeit komplett 12.07.2003 komplett Annahmeste - ArchiMeD

10.4 Cyclisierungen 285
10.4.3.19 3-Methoxy-11-methyl-11H-benzo[a]carbazol-5-carbonsäure-tert.-butylester
(121)
9
8
10
Summenformel: C23H23NO3
Molekulargewicht: 361.44
1' 1'' 2''
7 6
6b 6a 5
4a
4
11
10a 11a 11b 1'''
3
1
2
N
CH3
Einsatzmengen: 363 mg (1,0 mmol) 73
Iod
350 ml CH2Cl2
Reaktionsbedingungen: photochemisch hν, 1h
CO2C(CH3)3
OCH3
Aufarbeitung: säulenchromatographisch (PE / EE = 3 / 1)
Ausbeute: 52,1 mg (143 µmol; 14%)
Schmelzpunkt: 154-158°C, Zersetzung (Essigester/Hexan)
1 H-NMR δ [ppm]:
(300 MHz) Aceton-d6
13 C-NMR δ [ppm]:
(75 MHz) Aceton-d6
EI-MS (70 eV); m / z
(%)
1.73 (s, 9H, 3xCH3, 2''-H); 3.98 (s, 3H, CH3, 1'''-H); 4.39 (s,
3H, CH3, N-CH3); 7.27-7.34 (m, 2H, CH, 2-H, 8-H); 7.50
(ddd, 3 J=7.54, 3 J=8.29, 4 J=1.13, 1H, CH, 9-H); 7.69 (d,
3 J=8.29, 1H, CH, 10-H); 8.20 (d, 3 J=7.54, 1H, CH, 7-H);
8.78 (d, 3 J=3.77, 1H, CH, 1-H); 8.80 (d, 3 J=2.64, 1H, CH, 4-
H); 8.96 (s, 3H, CH3, 6-H)
29.6 (3xCH3, C-2''); 35.4 (CH3, N-CH3); 56.5 (CH3, C-1''');
82.0 (Cq, C-1''); 108.9 (CH, C-4); 111.5 (CH, C-10); 117.7
(Cq, C-5); 118.2 (CH, C-2); 119.3 (Cq, C-6a); 121.0 (CH, C-
7); 122.0 (Cq, C-11b); 122.1 (CH, C-8); 125.0 (Cq, C-6b);
126.2 (CH, C-1); 126.8 (CH, C-9); 127.0 (CH, C-6); 135.4
(Cq, C-4a); 139.9 (Cq, C-11a); 143.2 (Cq, C-10a); 159.6 (Cq,
C-3); 169.1 (Cq, C-1')
360.6 (_, 16.66), 304.7 (58.18), 289.7 (12.02), 261.7
(47.89), 246.9 (11.27), 217.8 (10.89), 106.7 (21.20), 85.8
(44.93), 80.8 (20.26), 76.6 (11.71), 69.8 (100.00), 60.8
(83.69), 58.0 (58.88)