Cholesterol → (3beta)-3-Hydroxycholest-5-en-7-one

HRID 650702Notes

Reaction equation

[CH3:1][CH:2]([CH2:4][CH2:5][CH2:6][C@H:7]([C@@H:9]1[C@:27]2([CH3:28])[C@H:12]([C@H:13]3[C@H:24]([CH2:25][CH2:26]2)[C@:22]2([CH3:23])[C:16]([CH2:17][C@H:18]([CH2:20][CH2:21]2)[OH:19])=[CH:15][CH2:14]3)[CH2:11][CH2:10]1)[CH3:8])[CH3:3].C([O:33]O)(C)(C)C.Cl[O-].[Na+]>ClCCl>[O:33]=[C:14]1[CH:15]=[C:16]2[C@:22]([CH3:23])([CH2:21][CH2:20][C@H:18]([OH:19])[CH2:17]2)[C@@H:24]2[C@@H:13]1[C@H:12]1[C@:27]([CH3:28])([CH2:26][CH2:25]2)[C@@H:9]([C@H:7]([CH3:8])[CH2:6][CH2:5][CH2:4][CH:2]([CH3:1])[CH3:3])[CH2:10][CH2:11]1

Participants

Conditions

Temperature: 2.5 °C

Procedure

Cholesterol (13, 1.93 gm, 0.005 mol) and tert-butyl hydroperoxide (4.2 ml of 70% aq. solution, 0.03 mol) were dissolved in dichloromethane (20 ml). The mixture was stirred vigorously, cooled to 0-5° C. and a dilute solution of sodium hypochlorite (15 ml, 5.25% available chlorine) was added slowly in the form of fine, small droplets during ten hours at 0-5° C. After completion of addition, the dichloromethane layer was separated, washed with water, aqueous sodium bisulfite solution (10%, 2×10 ml) and water. The organic solvent was evaporated under reduced pressure to yield a crude product, which was chromatographed on a silica gel column utilizing 20% acetone in petroleum-ether to afford 1.35 gm (67.5%) of 7-oxo-cholesterol (14) as a snow white solid having a melting point of 169-70° C.

Workup

additionAfter completion of addition
customthe dichloromethane layer was separated
washwashed with water, aqueous sodium bisulfite solution (10%, 2×10 ml) and water
customThe organic solvent was evaporated under reduced pressure
customto yield a crude product, which
customwas chromatographed on a silica gel column

Sources & evidence

ORD record: ord-48f33fd1ae1a4751af378fcb16d385a7
Source dataset: uspto-grants-2001_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06274746B1

Reaction notes

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