Diazomethane → HCID 14488066, compound

HRID 1614680Notes

Reaction equation

HRID 1614680 reaction equation
[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

Participants

3

Reactant 2

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

Product 1

HCID 14488066HCID 14488066, compound

Procedure

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).

Sources & evidence

ORD record
ord-b217864768b04e6c90f4a48557c53919
Source dataset
uspto-grants-1993_03
Patent number
US05198427

Reaction notes

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