Synthese und Transformationen chiraler 2,3 ...

192 V. Experimenteller Teil1 H-NMR (400 MHz, CDCl 3 ): δ [ppm] = 7.71 - 7.67, 7.51 - 7.45 (m, 5 H, CH-20,21,22,23,24), 3.85 (dd, 1 H, 3 J = 10.5 Hz, 3 J = 4.3 Hz, CH-16), 2.84 (s, 3 H, NCH 3 ), 2.51-2.43 (m, 1 H, CH 2 -17 A ), 2.24 - 2.16 (m, 1 H, CH 2 -17 B ), 1.94 - 0.90 (m, 8 H, Menthyl CH,CH 2 ), 0.93 (t, 3 H, 3 J = 7.5 Hz, CH 3 -18), 0.82 (d, 6 H, 3 J = 6.7 Hz, CH 3 -13/14,11) 0.48 (d,3 H, 3 J = 6.9 Hz, CH 3 -13/14), 0.48 (m, 1 H, CH Menthyl).13 C-NMR (100 MHz, CDCl 3 ): δ [ppm] = 165.4 (C-3), 162.2 (C-2), 143.3 (C-19), 135.3(C-22), 129.1 (C-21,23), 125.3 (C-20,24), 90.9 (C-5), 68.8 (C-16), 47.1 (C-6), 45.7 (C-10),34.8 (C-8), 29.4 (C-9), 25.4 (C-15), 24.3 (C-12), 23.3 (C-13/14), 22.6 (C-7), 22.1 (C-11),18.9 (C-13/14), 18.3 (C-17), 11.9 (C-18).IR (Film): ~ ν [cm -1 ] = 3060 (ν CH aromat.), 2950, 2920, 2870 (ν CH aliphat . ), 1700 (ν C=O,Lactam), 1650, 1630 (ν C=N), 1580 (ν C=C), 1050 (ν S=O), 750, 690 (δ CH oop monosubst.Aromat).MS (70 eV): m/z (%) = 388 (2.5) [M + ], 262 (100.0) [M + -PhSO], 179 (20.9), 151 (72.6)[C 8 H 11 N 2 O + ], 126 (43.2) [PhSOH + ], 78 (78.2) [C 6 H 6 + ].(5R,6S,9R)-6-Isopropyl-1,9-dimethyl-3-(1-ethyl-1-trans-propenyl)-1,4-diazaspiro[4.5]dec-3-en-2-on (36d)Die Verbindung wurde bei der Darstellung von 38c als Nebenprodukt erhalten.DC: R f = 0.62 (Ethylacetat/Cyclohexan = 2:1),UV, Iod