Acetone → HCID 44559609, compound

HRID 64986Notes

Reaction equation

HRID 64986 reaction equation
CCC/C=C/C=[CH:7]/[C:8]([O:10][C@@H:11]1[C@@:49]2([OH:51])[O:50][C@H:19]([CH2:20][CH:21]([C@H:62]([OH:64])[CH3:63])[O:22][C:23]([CH2:25][C@H:26]([OH:61])[CH2:27][C@H:28]3[O:33][C@@:32]([OH:54])([CH2:34][C@H:35]4[O:45][C@@H:44]([CH:46]=[CH:47][C:48]2([CH3:53])[CH3:52])[CH2:43]/[C:37](=[CH:38]\[C:39]([O:41][CH3:42])=[O:40])/[CH2:36]4)[C:31]([CH3:56])([CH3:55])[C@@H:30]([O:57][C:58]([CH3:60])=[O:59])[CH2:29]3)=[O:24])[CH2:18]/[C:12]/1=[CH:13]\[C:14]([O:16][CH3:17])=[O:15])=[O:9].[CH3:65][CH2:66][CH2:67]CCC.CC(C)=O>C(OCC)(=O)C>[CH3:63][C@@H:62]([OH:64])[C@@H:21]1[O:22][C:23](=[O:24])[CH2:25][C@H:26]([OH:61])[CH2:27][C@H:28]2[O:33][C@:32]([OH:54])([C:31]([CH3:55])([CH3:56])[C@@H:30]([O:57][C:58]([CH2:60][CH:66]([CH3:67])[CH3:65])=[O:59])[CH2:29]2)[CH2:34][C@H:35]2[O:45][C@H:44]([CH2:43]/[C:37](/[CH2:36]2)=[CH:38]\[C:39]([O:41][CH3:42])=[O:40])[CH:46]=[CH:47][C:48]([CH3:52])([CH3:53])[C@:49]2([OH:51])[O:50][C@H:19]([CH2:18]/[C:12](/[C@@H:11]2[O:10][C:8]([CH3:7])=[O:9])=[CH:13]\[C:14]([O:16][CH3:17])=[O:15])[CH2:20]1

Participants

5

Reactant 3

HCID 180AcetoneHCID 8058Hexane2×HCID 44277532Bryostatins

Product 1

HCID 44559609HCID 44559609, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

From a succession of silica gel column chromatographies and gel permeation (Sephadex LH-20) chromatography, an active fraction (0.38 g) was isolated as a white amorphous powder with PS ED50 =1.6×10-3 μg/ml and which contained bryostatins 4-7 by TLC (7:3 n-hexane:acetone and 2:3 n-hexane:ethyl acetate). By using dry column (2×60 cm) silica gel chromatographic methods with n-hexane:acetone (5:1→1:1) and n-hexane:ethyl acetate (2:1→1:2), six fractions were selected for further purification. The first fraction contained bryostatin 4. The second, third and fifth fractions were subjected to HPLC using Partisil-10M-9-ODS-2 (C-18 reversed phase) with a 1:1→9:1 methanol:water gradient (flow rate of 2 ml/min). The second fraction (15 mg) yielded pure bryostatin 5 (14.1 mg), melting at 169°-172° C. (needles from CH2Cl2 --CH3OH); FAB MS m/z 866 for C44H66O17 :[α]27D+106.92 (c=0.028, CH3OH); uv (CH3OH) λmax 226 nm (ε 36,300); and ir (KBr) 3465, 2980-2935, 1740, 1725, 1660-1640, 1440, 1385, 1370, 1290, 1230, 1165, 1100, 1080, 1060, and 1000 cm-1.

Workup

  1. dry with materialBy using dry column (2×60 cm) silica gel chromatographic methods with n-hexane:acetone (5:1→1:1) and n-hexane:ethyl acetate (2:1→1:2), six fractions
  2. customwere selected for further purification

Sources & evidence

ORD record
ord-9967a52714b24619ab051a6a5af308e8
Source dataset
uspto-grants-1986_09
Patent number
US04611066

Reaction notes

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