Hydrochloric Acid → 3-Hydroxy-26-oxo-22,26-epoxy-9,19-cyclolanost-24-en-28-oic acid

HRID 1614679ノート

反応式

HRID 1614679 の反応式
[CH3:1][C:2]1[C:7](=[O:8])[O:6][C@H:5]([C@H:9]([C@@H:11]2[C@@:15]3([CH3:45])[CH2:16][CH2:17][C@@:18]45[CH2:24][C@:23]64[CH2:25][CH2:26][C@H:27]([O:33][C@@H]4O[C@H](CO)[C@@H](O)[C@H](O)[C@H]4O)[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([CH3:46])[CH2:13][CH2:12]2)[CH3:10])[CH2:4][CH:3]=1.Cl>>[CH3:1][C:2]1[C:7](=[O:8])[O:6][C@H:5]([C@H:9]([C@@H:11]2[C@@:15]3([CH3:45])[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([CH3:46])[CH2:13][CH2:12]2)[CH3:10])[CH2:4][CH:3]=1

参加物

3

反応物 2

HCID 313Hydrochloric AcidHCID 6857683(20S,22S)-3β-(β-D-Glucopyranosyloxy)-22-hydroxy-9β,19-cyclolanost-24-ene-26,29-dioic acid δ-lactone

生成物 1

HCID 64510583-Hydroxy-26-oxo-22,26-epoxy-9,19-cyclolanost-24-en-28-oic acid収率 93.4%

実験手順

Abrusoside A [30 mg] is hydrolyzed by treatment with 1 N HCl (8 ml) for 4 hr at 100° C., to produce an aglycone, abrusogenin [21 mg], which is recrystallized from MeOH as colorless, needle-shaped crystals, and is shown to be homogeneous by tlc in solvent 2 (Rf 0.35), cyclohexaneEtOAc-CHCl3 -MeOH (6:4:2:3, solvent 5, Rf 0.49), and CHCl3 -MeOH (10:1, solvent 6, Rf 0.23). The H2O layer containing the saccharide portion of abrusoside A is neutralized with silver carbonate, with the filtrate subjected to gc/ms and tlc, and found to contain only D-glucose. Abrusogenin exhibited the following data: mp 278°-280°; [α]D +37° (c 0.1 CHCl3 -MeOH, 1:1), uv, (EtOH) end absorption; ir, vmax (KBr) 3430 (OH), 1707 (C=O), 1384, 1259, 1147, 1046 cm-1 ; 1H nmr, (360 MHz, CDCl3 +CD3OD) δ6.63 (1H, m, H-24), 4.50 (1H, dd, J=13.2 Hz, J=2.8 Hz, H-22), 4.09 (1H, dd, J=11.1 Hz, J=4.3 Hz, H-3), 2.58 (1H, m, H-23a), 1.91 (3H, br. s, 27-Me), 1.13 (3H, s, 30Me), 1.00 (3H, d, J=6.7 Hz, 21-Me), 0.97 (3H, s, 18-Me), 0.93 (3H, s, 28-Me), 0.61, 0.39 (2H, d, J=4.0 Hz, 19-H2) ppm; 13C nmr, (90.8 MHz, CDCl3) δ 180.19 (s, C-29), 167.13 (s, C-26), 140.29 (d, C-24), 127.96 (s, C-25), 80.51 (d, C-22), 75.22 (d, C-3), 54.57 (s, C-4), 48.87 (s, C-14), 47.92 (d, C-8), 47.54 (d, C-17), 45.24 (s, C-13), 44.10 (d, C-5), 40.02 (d, C-20), 35.44 (t, C-12), 32.68 (t, C-15), 31.58 (t, C-1), 29.92 (t, C-19), 29.21 (t, C-2), 27.86 (t, C-23), 27.58 (t, C-7), 26.37 (t, C-11), 25.60 (t, C-16), 25.09 (s, C-10), 23.00 (t, C-6), 19.95 (s, C-9), 19.37 (q, C-28), 17.89 (q, C-18), 17.07 (q, C-27), 12.85 (q, C-21), 9.18 (q, C-30) ppm; ei-ms, (70 eV) m/z 484 (M+, 10%), 469 (M+ -Me, 16), 466 (M+ -H2O, 19), 448 (17), 423 (11), 385 (19), 367 (11), 344 (10), 314 (81), 299 (18), 233 (28), 215 (22), 203 (15), 187 (28), 173 (38), 161 (44), 147 (52), 119 (59), 111 (58), 107 (81), 95 (100) 93 (67), 91 (38), 81 (50), 79 (32) 69 (24), 67 (25), 55 (80); hr-ms, mass measurement, found, 484.3189, (calcd. for C30H44O5, 484.3186); 367.2630, (C25H35O2, 367.2635); 314.2245, (C21H30O2, 314.224); 181.1223 , (C11H17O2, 181.1227); 167.1072, (C10H15O2, 167.1071); 139.0764, (C8H11O3, 139.0768); 111.0445, (C6H7O2, 111.0445);95.0131, (C5H3O2, 95.0133).

出典と根拠

ORDレコード
ord-a664c9a2c31541918d595e942f273ce5
出典データセット
uspto-grants-1993_03
特許番号
US05198427

反応ノート

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