Arbeit komplett 12.07.2003 komplett Annahmeste - ArchiMeD

10 Experimenteller, chemisch-präparativer Teil 208
Einsatzmengen: 2,02 g (9,7 mmol) 25
3,85 g (30,0 mmol) tert.-Butylacrylat
0,24 g (1,1 mmol) Pd(II)-acetat
3,40 g (20,4 mmol) Silberacetat
100 ml Eisessig
Schutzgas Argon
Reaktionsbedingungen: Variante A, Heck-Reaktion; 2 h erhitzen unter Rückfluß
Aufarbeitung: 1. säulenchromatographisch (PE / EE = 4 / 1)
2. säulenchromatographisch (PE / EE = 1 / 1)
Ausbeute: 0,24 g (0,7 mmol; 7%)
Schmelzpunkt: 126-127°C (Essigester/Hexan)
1 H-NMR δ [ppm]:
(300 MHz) Aceton-d6
13 C-NMR δ [ppm]:
(75 MHz) Aceton-d6
1.46 (s, 9H, 3xCH3, 2'''-H); 3.68 (s, 3H, CH3, N-CH3); 6.38
(d, 3 J=16.20, 1H, CH, 2''-H); 7.30 (ddd, 3 J=7.91, 3 J=7.16,
4 J=1.13, 1H, CH, 6-H); 7.35 (ddd, 3 J=8.29, 3 J=7.16,
4 J=1.51, 1H, CH, 5-H); 7.50-7.66 (m, 7H, 7xCH, 7-H, 2'-H,
3'-H, 4'-H, 5'-H, 6'-H, 3''-H); 7.97 (dd, 3 J=7.16, 4 J=1.13, 1H,
CH, 7-H)
29.4 (3xCH3, C-2'''); 32.4 (CH3, N-CH3); 80.5 (Cq, C-1''');
111.6 (Cq, C-3); 112.3 (CH, C-7); 116.0 (CH, C-2''); 122.1
(CH, C-4); 123.4 (CH, C-5); 124.7 (CH, C-6); 127.3 (Cq, C-
3a); 130.5 (2xCH, C-2' und C-6'); 131.0 (CH, C-4'); 132.1
(Cq, C-1'); 132.8 (2xCH, C-3' und C-5'); 139.3 (CH, C-3'');
140.0 (Cq, C-7a); 147.1 (Cq, C-2); 168.7 (Cq, C-1'')
EI-MS (70 eV); m/z (%) 332.5 (_, 62.56), 276.6 (85.90), 259.6 (31.99), 231.8
(100.00), 216.7 (52.52)
Elementaranalyse (%): Ber.: C: 79.25 H: 6.95 N: 4.20
Gef.: C: 77.99 H: 6.97 N: 4.09
UV/VIS [nm]: lgε
CH2Cl2
λmax: 235.8 (5.31); λ1: 340.6 (5.30); λ2: 284.2 (5.27)
IR (KBr); ö [cm -1 ] 3056 (w) 2978 (m) 2931 (w) 2904 (w) 1700 (s)
1620 (s) 1574 (w) 1519 (w) 1484 (m) 1470 (s)
1456 (m) 1442 (m) 1410 (m) 1393 (m) 1370 (s)
1356 (m) 1343 (m) 1309 (m) 1290 (s) 1256 (m)
1219 (m) 1166 (s) 1146 (s) 1134 (s) 1073 (s)
1043 (m) 1027 (m) 988 (m) 923 (w) 868 (m)
855 (m) 837 (w) 826 (m) 783 (w) 754 (m)
744 (m) 728 (m) 701 (m)