Arbeit komplett 12.07.2003 komplett Annahmeste - ArchiMeD

10.4 Cyclisierungen 259
IR (KBr); ö [cm -1 ] 3420 (w) 3069 (w) 3037 (w) 2984 (w) 2935 (w)
2908 (w) 2215 (m) 1713 (s) 1629 (w) 1599 (m)
1560 (w) 1501 (m) 1461 (m) 1422 (w) 1375 (m)
1342 (m) 1330 (m) 1312 (w) 1271 (s) 1252 (m)
1237 (s) 1211 (w) 1182 (w) 1155 (w) 1142 (m)
1109 (s) 1088 (s) 1054 (m) 1027 (w) 1017 (w)
958 (w) 921 (w) 909 (w) 876 (w) 841 (m)
781 (m) 767 (w) 751 (s) 723 (w)
10.4.2.5 3-Cyano-9-methyl-9H-carbazol-2-carbonsäure-tert.-butylester (102)
7
6
8
5
4b 4a
4
9
8a 9a
N
CH3
Summenformel: C19H18N2O2
Molekulargewicht: 306.36
Einsatzmengen: 308 mg (1,0 mmol) 60
Iod
350 ml CH2Cl2
Reaktionsbedingungen: photochemisch hν, 4h
3
1
CN
2
1'''
1'
1'' 2''
CO 2C(CH 3) 3
Aufarbeitung: säulenchromatographisch (PE / EE = 8 / 1)
Ausbeute: 27,0 mg (88,2 µmol; 9%)
Schmelzpunkt: 156-158°C (Essigester/Hexan)
1 H-NMR δ [ppm]:
(300 MHz) Aceton-d6
13 C-NMR δ [ppm]:
(75 MHz) Aceton-d6
1.56 (s, 9H, 3xCH3, 2''-H); 3.99 (s, 3H, CH3, N-CH3); 7.36
(ddd, 3 J=5.65, 3 J=6.03, 4 J=1.88, 1H, CH, 6H); 7.60-7.65 (m,
2H, 2xCH, 7-H, 8-H); 8.16 (s, 1H, CH, 1-H); 8.29 (d,
3 J=7.91, 1H, CH, 5-H); 8.57 (s, 1H, CH, 4-H)
29.2 (3xCH3, C-2''); 30.7 (CH3, N-CH3); 84.3 (Cq, C-1'');
103.4 (Cq, C-3); 111.6 (CH1, C-8); 113.8 (CH1, C-1); 120.7
(Cq, C-1'''); 122.5 (CH1, C-5); 122.9 (Cq, C-4a); 123.1 (CH1,
C-6); 126.6 (Cq, C-4b); 129.1 (CH1, C-4); 129.9 (CH1, C-7);
132.3 (Cq, C-2); 143.2 (Cq, C-9a); 143.8 (Cq, C-8a); 165.8
(Cq, C-1')