Diazomethane → HCID 14488066, Verbindung

HRID 1614680Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1614680
[CH3:1][C:2]1[C:7](=[O:8])[O:6][C@H:5]([C@H:9]([C@@H:11]2[C@@:15]3([CH3:34])[CH2:16][CH2:17][C@@:18]45[CH2:24][C@:23]64[CH2:25][CH2:26][C@H:27]([OH:33])[C@:28]([C:30]([OH:32])=[O:31])([CH3:29])[C@@H:22]6[CH2:21][CH2:20][C@H:19]5[C@:14]3([CH3:35])[CH2:13][CH2:12]2)[CH3:10])[CH2:4][CH:3]=1.[N+](=[CH2:38])=[N-]>>[CH3:1][C:2]1[C:7](=[O:8])[O:6][C@H:5]([C@H:9]([C@@H:11]2[C@@:15]3([CH3:34])[CH2:16][CH2:17][C@@:18]45[CH2:24][C@:23]64[CH2:25][CH2:26][C@H:27]([OH:33])[C@:28]([C:30]([O:32][CH3:38])=[O:31])([CH3:29])[C@@H:22]6[CH2:21][CH2:20][C@H:19]5[C@:14]3([CH3:35])[CH2:13][CH2:12]2)[CH3:10])[CH2:4][CH:3]=1

Komponenten

3

Edukt 2

HCID 9550DiazomethaneHCID 64510583-Hydroxy-26-oxo-22,26-epoxy-9,19-cyclolanost-24-en-28-oic acid

Produkt 1

HCID 14488066HCID 14488066, Verbindung

Versuchsvorschrift

Abrusogenin [10 mg] was methylated in ethereal diazomethane at room temperature overnight. On work-up, abrusogenin methyl ester [8 mg] was obtained as colorless prisms, after recrystallization in EtOAc, and was shown to be pure by tic in solvents 3 (Rf 0.71), 5 (Rf 0.56), and 6 (Rf 0.60). This derivative exhibited the following data: mp 246°-248°; [α]D +31.2° (c 0.08, CHCl3 -MeOH, 1:1); uv, (EtOH) end absorption; ir, νmax (KBr) 3529 (OH), 1710 (C=O), 1258, 1135, 1060, 1018 cm-1, 1H nmr, (360 MHz, CDCl3) δ 6.61 (1H, m, H-24), 4.50 (1H, dd, J=13.4 Hz, J=2.8 Hz, H-22), 4.10 (1H, dd, J=11.3 Hz, J=44 Hz, H-3), 3.71 (3H, s, 29-Ome), 2.57 (1H, m, H-23a), 1.91 (3H, br. s, 27-Me), 1.15 (3H, s, 30-Me), 1.00 (3H, d, J=6.8 Hz, 21-Me), 0.96 (3H, s, 18-Me), 0.93 (3H, s, 28-Me), 0.61, 0.39 (2H, d, J=4.2 Hz, 19-H2) ppm; 13C nmr, (90.8 MHz, CDCl3) δ 177.42 (s, C-29), 166.56 (s, C-26), 139.65 (d, C-24), 128.12 (s, C-25), 80.21 (d, C-22), 75.32 (d, C-3), 54.80 (s, C-4) 51.85 (q, 29-CH3), 48.79 (s, C-14), 47.85 (d, C-8), 47.42 (d, C-17), 45.20 (s, C-13), 44.30 (d, C-5), 40.05 (d, C-20), 35.40 (t, C-12), 32.58 (t, C-15), 31.43 (t, C-1), 29.88 (t, C-19), C-2), 27.85 (t, C-23), 27.55 (t, C-7), 26.32 (t, C-11), 25.52 (t, C-16), 25.04 (s, C-10), 23.07 (t, C-6), 19.91 (s, C-9), 19.38 (q, C-28), 17.86 (q, C-18), 17.14 (q, C-27), 12.82 (q, C-21), 9.26 (q, C-30) ppm; ei-ms, (70 ev) m/z 498 (M+, 1%), 480 (M+ -OH, 3), 465 (1), 448 (4), 421 (1), 367 (3), 314 (22), 299 (6), 247 (11), 215 (14), 199 (11), 173 (30), 147 (42), 133 (55), 119 (60), 111 (68), 107 (76), 105 (68), 95 (100) 81(72), 67 (39), 55 (48).

Quellen und Nachweise

ORD-Eintrag
ord-b217864768b04e6c90f4a48557c53919
Quelldatensatz
uspto-grants-1993_03
Patentnummer
US05198427

Notizen zur Reaktion

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