Ethanol → Vitamin D4

HRID 375989Notes

Reaction equation

HRID 375989 reaction equation
[CH3:1][C@@H:2]([C@@H:10]1[C@@:14]2([CH3:29])[CH2:15][CH2:16][C@@H:17]3[C@@:22]4([CH3:28])[CH2:23][CH2:24][C@H:25]([OH:27])[CH2:26][C:21]4=[CH:20][CH:19]=[C:18]3[C@@H:13]2[CH2:12][CH2:11]1)[CH2:3][CH2:4][C@@H:5]([CH:7]([CH3:9])[CH3:8])[CH3:6].O.C(O)C>C(OCC)C.C1C=CC=CC=1>[CH3:1][C@@H:2]([C@@H:10]1[C@@:14]2([CH3:29])[CH2:15][CH2:16][CH2:17]/[C:18](=[CH:19]\[CH:20]=[C:21]3\[CH2:26][C@@H:25]([OH:27])[CH2:24][CH2:23][C:22]\3=[CH2:28])/[C@@H:13]2[CH2:12][CH2:11]1)[CH2:3][CH2:4][C@@H:5]([CH:7]([CH3:8])[CH3:9])[CH3:6]

Participants

6

Reactant 3

HCID 702EthanolHCID 962WaterHCID 5326970Dihydroergosterol

Product 1

HCID 5460703Vitamin D4

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent

Procedure

22,23-dihydroergosterol (VIII) (2.0 g., 5.0 mmol.) was dissolved in a solution of diethyl ether and benzene (4:1, 600 ml.) and irradiated (Hannovia immersion lamp 450 watts) with stirring under argon in a water cooled quartz vessel for three hours. The solution was concentrated in vacuo to yield a gummy liquid, redissolved in 100 ml. of ethanol and heated at reflux under argon for eight hours. Then, the solution was concentrated in vacuo and the residue was adsorbed on a silica gel column and eluted with 30% ethyl acetate in hexane to afford Vitamin D4 (22,23-dihydroergocalciferol) (IX). 1.2 g. (60%). 1H NMR: (400 MHz, CDCl3), δppm 0.55 (3H, s, 18-H3) 0.78 (6H, dd, 26-H3 and 27-H3) 0.87 (3H, d, 21-H3) 0.93 (3H, d, 28-H3) 3.94 (1H, m, 3-H) 4.82 (1H, m (sharp), 19-H), 5.04 (1H, m (sharp), 19-H), 6.04 (1H, d, 7-H) 6.24 (1H, d, 6-H).

Workup

  1. customirradiated (Hannovia immersion lamp 450 watts)
  2. temperaturecooled quartz vessel for three hours
  3. concentrationThe solution was concentrated in vacuo
  4. customto yield a gummy liquid
  5. dissolutionredissolved in 100 ml
  6. temperatureat reflux under argon for eight hours
  7. concentrationThen, the solution was concentrated in vacuo
  8. washeluted with 30% ethyl acetate in hexane

Sources & evidence

ORD record
ord-6fc19a6008264c7eaa9e9c59834330aa
Source dataset
uspto-grants-1996_01
Patent number
US05488120

Reaction notes

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