p-Toluenesulfonic acid → HCID 14462265, compound

HRID 2395929Notes

Reaction equation

HRID 2395929 reaction equation
[C:1](OC(=O)C)(=[O:3])[CH3:2].C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH3:19][O:20][C:21]1[CH:38]=[CH:37][C:36]2[C@@H:35]3[C@H:26]([C@H:27]4[C@@:31]([CH2:33][CH2:34]3)([CH3:32])[C:30](=[O:39])[C:29]([CH3:40])=[CH:28]4)[CH2:25][CH2:24][C:23]=2[CH:22]=1.C(=O)(O)[O-].[Na+]>C(OC(C)=C)(=O)C>[C:1]([O:39][C:30]1[C@:31]2([CH2:33][CH2:34][C@H:35]3[C@@H:26]([CH2:25][CH2:24][C:23]4[CH:22]=[C:21]([O:20][CH3:19])[CH:38]=[CH:37][C:36]=43)[C:27]2=[CH:28][C:29]=1[CH3:40])[CH3:32])(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 7918Acetic AnhydrideHCID 516892Sodium BicarbonateHCID 57280791HCID 57280791, compound

Product 1

HCID 14462265HCID 14462265, compoundYield 87%

Reagents, catalysts & solvents 1

HCID 7916Isopropenyl acetateSolvent

Conditions

Temperature
100 °C

Procedure

Acetic anhydride (80 ml) and p-toluene sulfonic acid (6 g) are added to a suspension of 3-methoxy-16-methylestra-1,3,5(10),15-tetraen-17-one (1) (DE-OS 3,023,568 (1982)) (20 g; 67.7 mmol) in isopropenyl acetate (400 ml). The reaction mixture is stirred for about 20 hours at 100° C. After cooling it is poured on ice water and neutralized by addition of small portions of sodium bicarbonate. It is extracted three times with benzene, the combined organic phases are washed with water, dried on magnesium sulfate and concentrated by evaporation in a vacuum. The resulting brown residue (23.5 g) is chromatographed on silica gel with a mixture of ethyl acetate/benzene (1:49). The yellowish crystalline productis further purified by recrystallization of ethyl acetate/methanol. 19.8 g (87%) of colorless 14,16-diene-17-acetate (2) is obtained.

Workup

  1. temperatureAfter cooling it
  2. additionis poured on ice water
  3. extractionIt is extracted three times with benzene
  4. washthe combined organic phases are washed with water
  5. customdried on magnesium sulfate
  6. concentrationconcentrated by evaporation in a vacuum
  7. customThe resulting brown residue (23.5 g) is chromatographed on silica gel with a mixture of ethyl acetate/benzene (1:49)
  8. customThe yellowish crystalline productis further purified by recrystallization of ethyl acetate/methanol

Sources & evidence

ORD record
ord-e025cd617bb043eba0b7e9f9d29b9142
Source dataset
uspto-grants-1996_02
Patent number
US05491137

Reaction notes

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