Arbeit komplett 12.07.2003 komplett Annahmeste - ArchiMeD

10.4 Cyclisierungen 249
10.4.1 Synthese funktionalisierter 1,2-Dihydrocarbazole
10.4.1.1 Diethyl-9-methyl-2, 9-dihydro-1H-2,3-carbazoldicarboxylat (95)
8a
Summenformel: C19H21NO4
Molekulargewicht: 327.38
7
6
8
5
4b 4a
9
N
CH 3
Einsatzmengen: 327 mg (1,0 mmol) 53
50 ml Xylol
Reaktionsbedingungen: thermisch, 7h
4
9a
H
1
3
2
1''' 1 IV , 2 IV
CO 2C 2H 5
H
H
CO 2C 2H 5
1' 1'' 2''
Aufarbeitung: säulenchromatographisch (PE / EE = 4 / 1)
Ausbeute: 147 mg (449 µmol; 45%)
Schmelzpunkt: 130-132°C (Essigester/Hexan)
1 H-NMR δ [ppm]:
(300 MHz) Aceton-d6
13 C-NMR δ [ppm]:
(75 MHz) Aceton-d6
1.14 (t, 3 J=7.15, 3H, CH3, 2 IV -H); 1.31 (t, 3 J=7.15, 3H, CH3,
2''-H); 3.20 (dd, 2 J=17.41, 3 J=9.06, 1H, CH, 1-Ha); 3.64 (dd,
2 J=17.41, 3 J=2.86, 1H, CH2, 1-He); 3.78 (s, 3H, CH3, N-
CH3); 3.91-4.12 (m, 3H, CH2 und CH, 1''-H und 2-Ha); 4.24
(q, 3 J=7.15, 2H, CH2, 1 IV -H); 7.14 (ddd, 3 J=7.15, 3 J=5.48,
4 J=1.43, 1H, CH, 6-H); 7.18 (ddd, 3 J=6.91, 3 J=5.72,
4 J=1.43, 1H, CH, 7-H); 7.42 (dd, 3 J=7.15, 4 J=1.91, 1H, CH,
8-H); 7.69 (dd, 3 J=6.20, 4 J=1.67, 1H, CH, 5-H; 7.96 (s, 1H,
CH, 4-H)
15.3 (2xCH3, C-2''); 15.7 (CH3, C-2 lV ); 25.5 (CH2, C-1); 30.9
(CH3, N-CH3); 40.9 (CH, C-2); 61.4 (CH2, C-1''); 62.2 (CH2,
C-1 lV ); 110.5 (Cq, C-3); 111.7 (CH, C-8); 118.7 (Cq, C-4a);
119.3 (CH1, C-5); 122.6 (CH, C-6); 123.4 (CH, C-7); 127.0
(Cq, C-4b); 133.3 (CH, C-4); 140.0 (Cq, C-9a); 141.8 (Cq, C-
8a); 168.3 (Cq, C-1'''); 174.5 (Cq, C-1')
EI-MS (70 eV); m/z (%) 326.5 (_, 56.81), 253.9 (89.80), 225.8 (22.78), 207.7
(63.29), 180.6 (100.00), 166.6 (20.64), 151.5 (10.09), 106.4
(16.98), 43.5 (12.28)