Tetrahydrofuran → 3-Methoxyestra-3,5(10)-dien-17beta-ol

HRID 649744

Reaction equation

HRID 649744 reaction equation
[CH3:1][O:2][C:3]1[CH2:4][C:5]2[CH2:6][CH2:7][C@@H:8]3[C@@H:17]([C:18]=2[CH2:19][CH:20]=1)[CH2:16][CH2:15][C@@:13]1([CH3:14])[C@H:9]3[CH2:10][CH2:11][C@@H:12]1[OH:21].O1CCCC1.CC([O-])(C)C.[K+]>CS(C)=O>[CH3:1][O:2][C:3]1[CH2:20][CH2:19][C:18]2[C@@H:17]3[C@H:8]([C@H:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C@@H:12]([OH:21])[CH2:11][CH2:10]4)[CH2:7][CH2:6][C:5]=2[CH:4]=1

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 1019633-Methoxyestra-2,5(10)-dien-17beta-olHCID 23665647Potassium tert-butoxide

Product 1

HCID 106133673-Methoxyestra-3,5(10)-dien-17beta-olYield 65.3%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

3-Methoxyestra-2,5(10)-dien-17β-ol 1 (2.0 g, 6.9 mmol) was added to a solution consisting of tetrahydofuran (15 ml), DMSO (5 ml) and t-BuOK (20.7 mmol). The resultant solution was stirred at ambient temperature for 10 hours at which time the solution was concentrated to Å5 ml and chromatographically filtered with 50% ethylether/petroleum ether (light) through 10 g of silica gel. The subsequent dimethyl sulfoxide (DMSO) free -powder was flash chromatographed affording 4 as white needles (1.30 g, 65% conversion, 91% based on recovered 1), Alternatively, crystallization by selective seeding (ether/methanol) was utilized, thereby circumventing chromatographic purification. 1H NMR (d6-acetone) δ4.629 (s, 1H), 3.505 (t, J=8.09 Hz, 1H), 3.431 (s, 3H), 2.15-0.98 (complex, 20H), 0.644 (s, 3H). 13C NMR (CDCl3) δ156.71, 126.56, 123.88, 96.55, 81.31, 54.19, 50.18, 46.03, 39.91, 37.54, 30.64, 30.58, 30.21, 27.71, 27.17, 25.67, 25.24, 23.22, 11.37.

Workup

  1. concentrationwas concentrated to Å5 ml
  2. filtrationchromatographically filtered with 50% ethylether/petroleum ether (light) through 10 g of silica gel
  3. customchromatographed

Sources & evidence

ORD record
ord-1c064eb3c71342cebdb773f9121df67f
Source dataset
uspto-grants-2001_08
Patent number
US06271220B1

Linked notes

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