Diazald → Methyl chenodeoxycholate

HRID 258236

Reaction equation

HRID 258236 reaction equation
[CH3:1][C@@H:2]([C@@H:8]1[C@@:12]2([CH3:28])[CH2:13][CH2:14][C@@H:15]3[C@@:20]4([CH3:26])[CH2:21][CH2:22][C@@H:23]([OH:25])[CH2:24][C@H:19]4[CH2:18][C@@H:17]([OH:27])[C@H:16]3[C@@H:11]2[CH2:10][CH2:9]1)[CH2:3][CH2:4][C:5]([OH:7])=[O:6].[N+](=[CH2:31])=[N-].CC1C=CC(S(N(N=O)C)(=O)=O)=CC=1>C1COCC1.CCOCC>[CH3:1][C@@H:2]([C@@H:8]1[C@@:12]2([CH3:28])[CH2:13][CH2:14][C@@H:15]3[C@@:20]4([CH3:26])[CH2:21][CH2:22][C@@H:23]([OH:25])[CH2:24][C@H:19]4[CH2:18][C@@H:17]([OH:27])[C@H:16]3[C@@H:11]2[CH2:10][CH2:9]1)[CH2:3][CH2:4][C:5]([O:7][CH3:31])=[O:6]

Participants

6

Reactant 3

HCID 6628DiazaldHCID 9550DiazomethaneHCID 10133Chenodeoxycholic Acid

Product 1

HCID 11069533Methyl chenodeoxycholate

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

Chenodeoxycholic acid (0.5 g, 1.3 mmol) in THF (10 ml) at 0° C. was treated dropwise with freshly prepared diazomethane in ether (prepared in the usual manner from diazald) until the yellow colour persisted. After 15 minutes at 0° C. the solvent was evaporated to yield a white foam (0.55 g). The compound would not recrystallise, although gas chromatography showed the product to be 97% pure. The product was further purified by preparative silica tlc. (solvent system: EtOAc/CH2Cl2 /AcOH--10:10:1) to afford pure methyl chenodeoxycholate3 (0.42 g, 81%) as a foam: 1H NMR (60 MHz; CDCl3) δ0.65 (3H, s, 18-CH3), 0.91 (3H, s, 19-CH3), 1.85 (2H, s [exchanges on adding D2O], 3α and 7α OH's), 3.1-3.7 (1H, m, 3β-H), 3.64 (3H, s, --OMe), 3.7-3.9 (1H, m, 7β-H); IR (nujol mull) 3384 (OH's), 1740 (C=O) cm-1 ; MS: Found m/z 406.3077; C25H42O4 (M) requires 406.3083.

Workup

  1. customAfter 15 minutes at 0° C. the solvent was evaporated

Sources & evidence

ORD record
ord-7455755d994241eb835eee7db5692e4b
Source dataset
uspto-grants-1993_11
Patent number
US05266566

Linked notes

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