Trimethyl orthoformate → 3-Ethylenedioxy-11beta-fluoro-7alpha-methylestr-5(10)-en-17beta-ol

HRID 900678Notes

Reaction equation

HRID 900678 reaction equation
[CH:1]([O:6][CH3:7])(OC)OC.O.[C:9]1(C)C=CC(S(O)(=O)=O)=CC=1.[F:20][C@H:21]1[CH2:38][C@@:36]2([CH3:37])[C@@H:32]([CH2:33][CH2:34][C@@H:35]2[OH:39])[C@H:31]2[C@H:22]1[C@@H:23]1[C:28]([CH2:29][C@H:30]2[CH3:40])=[CH:27][C:26](=[O:41])C[CH2:24]1.C(=O)([O-])[O-].[Na+].[Na+]>ClCCl.C(OCC)(=O)C.C(O)CO>[CH2:9]1[CH2:7][O:6][CH:1]2[CH:26]([CH2:27][C:28]3[CH2:29][C@@H:30]([CH3:40])[C@@H:31]4[C@@H:22]([C:23]=3[CH2:24]2)[C@@H:21]([F:20])[CH2:38][C@@:36]2([CH3:37])[C@H:32]4[CH2:33][CH2:34][C@@H:35]2[OH:39])[O:41]1

Participants

8

Reactant 4

HCID 9005Trimethyl orthoformateHCID 10340Sodium CarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 990463811beta-Fluoro-17beta-hydroxy-7alpha-methylestr-4-en-3-one

Product 1

HCID 865974503-Ethylenedioxy-11beta-fluoro-7alpha-methylestr-5(10)-en-17beta-ol

Reagents, catalysts & solvents 3

HCID 174Ethylene GlycolSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

3.63 ml of ethylene glycol and 1.82 ml of trimethyl orthoformate and 23.6 ml of para-toluenesulfonic acid hydrate were added to a solution of 500 mg of 11β-fluoro-17β-hydroxy-7α-methyl-estr-4-en-3-one (I) in 6.35 ml of dichloromethane. The reaction mixture was stirred for 20 hours at room temperature. Then, it was mixed with sodium carbonate solution, diluted with ethyl acetate, washed neutral, dried on sodium sulfate, concentrated by evaporation in a vacuum and chromatographed on silica gel with hexane/ethyl acetate. 170 mg of 3-ethylenedioxy-11β-fluoro-7α-methylestr-5(10)-en-17β-ol (C), which contained portions of double-bond-isomeric 3-ethylenedioxy-11β-fluoro-7α-methylestr-5-en-17β-ol (C), was obtained.

Workup

  1. washwashed neutral
  2. customdried on sodium sulfate
  3. concentrationconcentrated by evaporation in a vacuum
  4. customchromatographed on silica gel with hexane/ethyl acetate
  5. customwas obtained

Sources & evidence

ORD record
ord-855d177f12974593abd7ebbbd9a30865
Source dataset
uspto-grants-2008_04
Patent number
US07361645B2

Reaction notes

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