Sodium Thiosulfate → HCID 70167631, compound

HRID 1069056Notes

Reaction equation

HRID 1069056 reaction equation
[C:1]([O:9][C@H:10]1[CH2:36][CH2:35][C@@:34]2([CH3:37])[C:12](=[CH:13][CH2:14][C@@H:15]3[C@@H:33]2[CH2:32][CH2:31][C@@:30]2([CH3:38])[C@H:16]3[CH2:17][CH2:18][C@@H:19]2[C@@H:20]([O:22][Si:23]([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24])[CH3:21])[C:11]1([CH3:40])[CH3:39])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.BrN1C(=O)CCC1=O.S([O-])([O-])(=O)=S.[Na+].[Na+].C(N(CC)C(C)C)(C)C>C1CCCCC1.C1(C)C=CC=CC=1>[C:1]([O:9][C@H:10]1[CH2:36][CH2:35][C@@:34]2([CH3:37])[C:12](=[CH:13][CH:14]=[C:15]3[C@@H:33]2[CH2:32][CH2:31][C@@:30]2([CH3:38])[C@H:16]3[CH2:17][CH2:18][C@@H:19]2[C@@H:20]([O:22][Si:23]([C:26]([CH3:28])([CH3:29])[CH3:27])([CH3:25])[CH3:24])[CH3:21])[C:11]1([CH3:39])[CH3:40])(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 24477Sodium ThiosulfateHCID 67184N-bromobutanimide2×HCID 81531DiisopropylethylamineHCID 70166378HCID 70166378, compound

Product 1

HCID 70167631HCID 70167631, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8078CyclohexaneSolvent

Procedure

xi)—A mixture of (3β,20S)-20-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-4,4-dimethylpregn-5-en-3-ol benzoate (44.6), dry toluene (394 ml), dry cyclohexane (394 ml) and N-bromosuccinimide (17.8 g) was heated at reflux temperature for 10 min. The reaction mixture was cooled, another portion of N-bromosuccinimide (17.8 g) was added, and reflux was continued for another 10 min. The reaction mixture was cooled, a saturated aqueous solution of sodium thiosulfate (802 ml) was added and the resulting mixture was stirred for 30 min. The organic phase and the aqueous phase were separated and the latter extracted two times with toluene. The combined organic phases were dried over sodium sulfate and concentrated under reduced pressure. A solution of the crude product thus obtained in dry toluene (1381 ml) and N,N-diisopropylethylamine (138 ml) was heated under reflux for 1.5 h. Then it was cooled and washed with a saturated aqueous solution of sodium hydrogen carbonate, a saturated aqueous solution of ammonium chloride and with brine, the aqueous phase each time being extracted with ethyl acetate. The combined toluene and ethyl acetate solutions were dried over sodium sulfate and concentrated under reduced pressure. Column chromatography afforded (3β,20S)-20-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-4,4-dimethylpregna-5,7-dien-3-ol benzoate (compound 12a; 40.0 g).

Workup

  1. temperaturewas heated
  2. temperatureat reflux temperature for 10 min
  3. temperatureThe reaction mixture was cooled
  4. temperaturereflux
  5. temperatureThe reaction mixture was cooled
  6. customThe organic phase and the aqueous phase were separated
  7. extractionthe latter extracted two times with toluene
  8. dry with materialThe combined organic phases were dried over sodium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customA solution of the crude product thus obtained in dry toluene (1381 ml)
  11. temperatureunder reflux for 1.5 h
  12. temperatureThen it was cooled
  13. washwashed with a saturated aqueous solution of sodium hydrogen carbonate
  14. extractiona saturated aqueous solution of ammonium chloride and with brine, the aqueous phase each time being extracted with ethyl acetate
  15. dry with materialThe combined toluene and ethyl acetate solutions were dried over sodium sulfate
  16. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-ba890d855052474799c3b70835e45130
Source dataset
uspto-grants-2001_06
Patent number
US06251887B1

Reaction notes

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