Thiophenol → HCID 86738655, compound

HRID 2199087Notes

Reaction equation

HRID 2199087 reaction equation
[C:1]([O:4][C@H:5]1[CH2:22][C@@:20]2([CH3:21])[C@@H:16]([CH2:17][CH:18]=[C:19]2[S:23][CH2:24][CH3:25])[C@H:15]2[C@@:6]1([F:28])[C@:7]1([CH3:27])[C:12]([CH2:13][CH2:14]2)=[CH:11][C:10](=[O:26])[CH:9]=[CH:8]1)(=[O:3])[CH3:2].[C:29]1([SH:35])[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.B(F)(F)F.CCOCC>ClCCl.C(Cl)(Cl)Cl.CCCCCC>[C:1]([O:4][C@H:5]1[CH2:22][C@@:20]2([CH3:21])[C@@H:16]([CH2:17][CH2:18][C:19]2([S:23][CH2:24][CH3:25])[S:35][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C@H:15]2[C@@:6]1([F:28])[C@:7]1([CH3:27])[C:12]([CH2:13][CH2:14]2)=[CH:11][C:10](=[O:26])[CH:9]=[CH:8]1)(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 7969ThiophenolHCID 8000Boron trifluoride etherateHCID 67880269HCID 67880269, compound

Product 1

HCID 86738655HCID 86738655, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 21585165Chloroform hexaneSolvent

Procedure

A solution of 1.2 g (2.97 mmole) of 11β-acetyloxy-17-(ethylthio)-9-fluoroandrosta-1,4,16-trien-3-one, 18 ml of dry dichloromethane and 0.8 ml of thiophenol is cooled to -20° C. under nitrogen. Boron trifluoride etherate (0.6 ml) is then added. The solution is stirred at -10° to -20° C. for 2 hours under nitrogen. The resulting solution is diluted with dichloromethane, washed with saturated sodium bicarbonate and water, dried over anhydrous Na2SO4 and evaporated in vacuo to give a gum. This is dissolved in chloroform-hexane (1:1) and chromatographed on a 20 g-silica gel column, eluting successively with chloroform-hexane (1:1), chloroform, chloroform-ethyl acetate (95:5) and chloroform-methanol (9:1) to give 1.0 g of impure title compound. This is dissolved in the minimum amount of ethyl acetate and stood at room temperature for 2 days. The solid that precipitates is filtered to give 480 mg of title compound, melting point 152°-158° C., with consistent spectral data.

Workup

  1. washwashed with saturated sodium bicarbonate and water
  2. dry with materialdried over anhydrous Na2SO4
  3. customevaporated in vacuo
  4. customto give a gum
  5. customchromatographed on a 20 g-silica gel column
  6. washeluting successively with chloroform-hexane (1:1), chloroform, chloroform-ethyl acetate (95:5) and chloroform-methanol (9:1)

Sources & evidence

ORD record
ord-97acca9bc104496c9c69d33020a8c64e
Source dataset
uspto-grants-1982_11
Patent number
US04361559

Reaction notes

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