Arbeit komplett 12.07.2003 komplett Annahmeste - ArchiMeD

10.3 Cyclisierungsedukte 201
Einsatzmengen: 1,00 g (5,4 mmol) 20
6,24 g (16,0 mmol) Benzyltriphenylphosphoniumchlorid
10 ml (16,0 mmol) 1,6 M n-Butyllithiumlösung in n-Hexan-
Lösung
70 ml absolutes DME
Schutzgas Argon
Reaktionsbedingungen: 2 h rühren bei Raumtemperatur
Aufarbeitung: säulenchromatographisch (PE / EE = 3 / 2)
Ausbeute: 0,51 g (1,51 mmol, 28%), Lit. 193 : 28%
Schmelzpunkt: 166-169°C (Essigester/Hexan) Lit. 193 : 191-196°C (n-Hexan)
1 H-NMR δ [ppm]:
(300 MHz)
Aceton-d6 / CD2Cl2
13 C-NMR δ [ppm]:
(75 MHz)
Aceton-d6 / CD2Cl2 / DMSO-d6
3.84 (s, 3H, CH3, N-CH3); 7.00 (d, 3 J=16.2, 1H, CH (Vinyl-
H), 1'''-H o. 2'''-H o. 1 IV -H o. 2 IV -H; ((E/E)-Isomer)); 7.15-
7.64 (m, 16H, 13xCH und 3xCH (Vinyl-H), 5-H, 6-H, 7-H,
2'-H, 3'-H, 4'-H, 5'-H, 6'-H, 2''-H, 3''-H, 4''-H, 5''-H, 6''-H, 1'''-
H o. 2'''-H o. 1 IV -H o. 2 IV -H); 8.03 (d, 3 J=7.91, 1H, CH, 4-H)
31.9 (CH3, N-CH3); 110.8 (CH, C-7); 113.9 (Cq, C-3); 118.3
(CH, C-1'''); 121.6 (2xCH, C-4' und C-4''); 123.7 (CH, C-4);
124.0 (CH, C-5); 126.9 (2xCH, C-2' und C-6'); 127.0 (Cq, C-
3a); 127.6 (CH, C-6); 127.7 (CH, C-1 lV ); 127.9 (2xCH, C-2''
und C-6''); 129.4 (CH, C-2'''); 129.8 (2xCH, C-3' und C-5');
130.0 (2xCH, C-3'' und C-5''); 136.9 (CH, C-2 lV ); 138.4 (Cq,
C-7a); 138.8 (Cq, C-1''); 139.6 (Cq, C-1'); 140.2 (Cq, C-2)
EI-MS (70 eV); m/z (%) 335.1 (_, 31.32), 306.9 (27.23), 276.8 (38.86), 258.2
(28.29), 247.9 (34.19), 203.6 (19.49), 148.7 (52.28), 128.2
(25.87), 106.9 (84.73), 76.6 (100.00)
Elementaranalyse (%): Ber.: C: 89.51 H: 6.31 N: 4.18
Gef.: C: 87.71 H: 6.15. N: 3.59
UV/VIS [nm]: lgε
CH2Cl2
λmax: 318.8 (5.77), λ1: 278.2 (5.58)
IR (KBr), ö [cm -1 ] 3080 (w) 3060 (w) 3030 (w) 3000 (w) 1590 (w)
1470 (w) 1440 (s) 1400 (w) 1370 (w) 1350 (w)
1315 (w) 1280 (w) 1190 (s) 1165 (m) 1125 (s)
1095 (m) 1075 (m) 1030 (w) 1000 (w) 975 (w)
950 (w) 940 (w) 865 (w) 765 (m) 760 (s)
750 (m) 725 (s) 700 (s) 620 (w) 550 (s)