p-Toluenesulfonic acid → 3beta-Acetoxy-1alpha,2alpha-epoxy-7alpha-hydroxypregn-5-ene-20-carbaldehyde

HRID 1196341Notes

Reaction equation

HRID 1196341 reaction equation
[C:1]([O:4][C@H:5]1[C@@H:31]2[O:32][C@@H:30]2[C@@:29]2([CH3:33])[C:7](=[CH:8][C@@H:9]([OH:35])[C@@H:10]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:34])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[CH:15]([CH:17]2OCC(C)(C)C[O:18]2)[CH3:16])[CH2:6]1)(=[O:3])[CH3:2].C1(C)C=CC(S(O)(=O)=O)=CC=1.C(OCC)(=O)C.CCCCCC>CC(C)=O>[C:1]([O:4][C@H:5]1[C@@H:31]2[O:32][C@@H:30]2[C@@:29]2([CH3:33])[C:7](=[CH:8][C@@H:9]([OH:35])[C@@H:10]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:34])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[CH:15]([CH:17]=[O:18])[CH3:16])[CH2:6]1)(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 21226206Ethyl acetate hexaneHCID 8674580220-(5,5-Dimethyl-1,3-dioxan-2-yl)-1alpha, 2alpha-epoxy-7alpha-hydroxypregna-5-en-3beta-yl acetate

Product 1

HCID 867458133beta-Acetoxy-1alpha,2alpha-epoxy-7alpha-hydroxypregn-5-ene-20-carbaldehydeYield 67.1%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent2×

Procedure

In 4 ml of acetone was dissolved 4.9 mg (0.01 mmole) of 20-(5,5-dimethyl-1,3-dioxan-2-yl)-1α,2α-epoxy-7α-hydroxypregn-5-en-3β-yl acetate, followed by addition of 1 ml of a 1 mmol/1 solution of p-toluenesulfonic acid in acetone (containing 0.001 mmole of p-toluenesulfonic acid). The mixture was stirred at room temperature for 12 hours. From the reaction mixture thus obtained, the solvent was distilled off under reduced pressure and the residue was diluted with methylene chloride. This methylene chloride solution was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution and dried over magnesium sulfate. The solvent was then distilled off under reduced pressure and the residue was purified by silica gel chromatography (eluent: ethyl acetate-hexane =1:5, v/v) to recover 2.7 mg of 3β-acetoxy-1α,2α-epoxy-7α-hydroxypregn-5-ene-20-carbaldehyde (yield: 67%).

Workup

  1. customFrom the reaction mixture thus obtained
  2. distillationthe solvent was distilled off under reduced pressure
  3. additionthe residue was diluted with methylene chloride
  4. washThis methylene chloride solution was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution
  5. dry with materialdried over magnesium sulfate
  6. distillationThe solvent was then distilled off under reduced pressure
  7. customthe residue was purified by silica gel chromatography (eluent

Sources & evidence

ORD record
ord-b1c677ae092242ddae0be2aedf9f9a88
Source dataset
uspto-grants-1992_05
Patent number
US05112998

Reaction notes

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