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

HRID 1614679Notes

Reaction equation

HRID 1614679 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([CH3:45])[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

Participants

3

Reactant 2

HCID 313Hydrochloric AcidHCID 6857683124962-06-7

Product 1

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

Procedure

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).

Sources & evidence

ORD record
ord-a664c9a2c31541918d595e942f273ce5
Source dataset
uspto-grants-1993_03
Patent number
US05198427

Reaction notes

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