Isopropenyl acetate → 2-Methoxy-3,17-diacetoxyestra-1,3,5(10),14,16-pentaene

HRID 1357475Notes

Reaction equation

HRID 1357475 reaction equation
O.C1(C)C(S(O)(=O)=O)=CC=CC=1.[CH3:13][O:14][C:15]1[C:16]([OH:34])=[CH:17][C:18]2[CH2:19][CH2:20][C@@H:21]3[C@@H:30]([C:31]=2[CH:32]=1)[CH2:29][CH2:28][C@@:26]1([CH3:27])[C@H:22]3[CH:23]=[CH:24][C:25]1=[O:33].[C:35](OC(C)=C)(=[O:37])[CH3:36].[C:42](OC(=O)C)(=[O:44])[CH3:43]>C(Cl)Cl.CC(C)=O>[CH3:13][O:14][C:15]1[C:16]([O:34][C:42](=[O:44])[CH3:43])=[CH:17][C:18]2[CH2:19][CH2:20][C@@H:21]3[C@@H:30]([C:31]=2[CH:32]=1)[CH2:29][CH2:28][C@@:26]1([CH3:27])[C:22]3=[CH:23][CH:24]=[C:25]1[O:33][C:35](=[O:37])[CH3:36]

Participants

7

Reactant 4

HCID 7916Isopropenyl acetateHCID 7918Acetic AnhydrideHCID 124969952-Methylbenzenesulfonic acid hydrateHCID 211357012-Methoxyestra-1,3,5(10),15-tetraen-3-ol-17-one

Product 1

HCID 113265312-Methoxy-3,17-diacetoxyestra-1,3,5(10),14,16-pentaeneYield 80.8%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 6344DichloromethaneSolvent

Procedure

Under nitrogen, toluenesulfonic acid monohydrate (0.1 g, 0.53 mmol) was added to a solution of 2-Methoxyestra-1,3,5(10),15-tetraen-3-ol-17-one prepared in Example 3 (0.25 g, 0.84 mmol), isopropenyl acetate (5 mL, 45.15 mmol) and acetic anhydride (5 mL, 53 mmol) and the mixture was heated to reflux for 6 h. At the end of that time, analysis by tlc (2% acetone in CH2Cl2) indicated a complete reaction. The reaction was cooled to room temperature, poured into ice water (˜100 mL) and stirred for 1 h. The mixture was extracted with methylene chloride (3x). The organic fractions were washed with water (1x), saturated sodium bicarbonate solution (1x) and water (1x), filtered through anhydrous sodium sulfate, combined and concentrated in vacuo. The residue was crystallized from methanol to give the pure diacetate (17) (0.259 g, 80.8%).

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 6 h
  3. customa complete reaction
  4. extractionThe mixture was extracted with methylene chloride (3x)
  5. washThe organic fractions were washed with water (1x), saturated sodium bicarbonate solution (1x) and water (1x)
  6. filtrationfiltered through anhydrous sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe residue was crystallized from methanol

Sources & evidence

ORD record
ord-b12bbfe5a68b46f382406ef47271b6fb
Source dataset
uspto-grants-2003_07
Patent number
US06593321B2

Reaction notes

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