Methanesulfonyl chloride → HCID 53691273, compound

HRID 2420237Notes

Reaction equation

HRID 2420237 reaction equation
O[C@:2]12[CH2:19][CH:18]=[CH:17][CH2:16][C@:15]1([CH3:20])[C@@H:14]1[C@H:5]([C@H:6]3[C@@:10]([CH2:12][CH2:13]1)([CH3:11])[C:9]([Br:21])=[CH:8][CH2:7]3)[CH2:4][C@H:3]2[OH:22].CS(Cl)(=O)=O.O[C@]12CC=CC[C@]1(C)[C@@H]1[C@H]([C@H]3[C@@](CC1)(C)C(Br)=CC3)C[C@H]2Cl>>[O:22]1[C@H:3]2[CH2:4][C@@H:5]3[C@@H:14]([C@@:15]4([CH3:20])[CH2:16][CH:17]=[CH:18][CH2:19][C@:2]124)[CH2:13][CH2:12][C@@:10]1([CH3:11])[C@H:6]3[CH2:7][CH:8]=[C:9]1[Br:21]

Participants

4

Reactant 3

HCID 31297Methanesulfonyl chlorideHCID 54276311HCID 54276311, compoundHCID 70614858HCID 70614858, compound

Product 1

HCID 53691273HCID 53691273, compoundYield 89%

Procedure

95 g (0.258 mole) of 5α,6β-dihydroxy-17-bromo-androsta-2,16-diene obtained as described in section (b) of Example 2 are reacted with 21 ml (0.276 mole) of methanesulfonic acid chloride, as described in section (c) of Example 2, but with the difference that the mixture of products obtained after evaporation of the dichloro methane extract is dissolved in 16-fold amount (calculated on the starting material) of ethanol and the 12% aqueous solution of 19 g of sodium hydroxide is added to the ethanolic solution. The reaction mixture is heated to reflux for 10 minutes, then cooled to room temperature and the pH value is adjusted to 7 with acetic acid. The solvent is then distilled off, the evaporation residue is triturated with water. The precipitated product is filtered off, washed with water until the washings are neutral and dried over phosphorous pentoxide in vacuo. The obtained product is recrystallized from acetonitrile. Yield: 89% of 5α,6α-epoxy-17-bromo-androsta-2,16-diene; m.p. 146°-147° C; [α]D25 = - 18.3° (c = 1 in chloroform).

Workup

  1. additionwith the difference that the mixture of products
  2. customobtained
  3. customafter evaporation of the dichloro methane
  4. extractionextract
  5. dissolutionis dissolved in 16-fold amount (
  6. additionthe 12% aqueous solution of 19 g of sodium hydroxide is added to the ethanolic solution
  7. temperatureThe reaction mixture is heated
  8. temperatureto reflux for 10 minutes
  9. distillationThe solvent is then distilled off
  10. customthe evaporation residue is triturated with water
  11. filtrationThe precipitated product is filtered off
  12. washwashed with water until the washings
  13. dry with materialdried over phosphorous pentoxide in vacuo
  14. customThe obtained product is recrystallized from acetonitrile

Sources & evidence

ORD record
ord-dbe9f1bd86e34a0995e93c7168acc8c3
Source dataset
uspto-grants-1978_08
Patent number
US04110326

Reaction notes

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