Butanethiol → HCID 86738656, compound

HRID 2199090Notes

Reaction equation

HRID 2199090 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].[CH2:29]([SH:33])[CH2:30][CH2:31][CH3:32]>>[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:33][CH2:29][CH2:30][CH2:31][CH3:32])[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]

Participants

3

Reactant 2

HCID 8012ButanethiolHCID 67880269HCID 67880269, compound

Product 1

HCID 86738656HCID 86738656, compoundYield 81.8%

Conditions

Temperature
10 °C

Procedure

A solution of 11β-acetyloxy-17-(ethylthio)-9-fluoroandrosta-1,4,16-triene-3-one (700 mg; see example 11c) and n-butanethiol (271 mg) is cooled and stirred in a bath at -40° to -45° C. and distilled boron trifluoride etherate (0.3 ml) is added. After 2.0 hours at -40° to -45° C., the solution is gradually warmed to 10° C. in the course of 1.5 hours. The mixture is then diluted with dichloromethane, washed successively with a saturated sodium bicarbonate solution and brine, dried (MgSO4 anh.) and is evaporated to afford the crude title compound. This material is chromatographed over a column of silica gel (20 g), eluting the column with chloroform-hexane mixtures (1:1, 1:4), chloroform and chloroform-ethyl acetate (95:5) to afford the title compound (700 mg). Examination of the nmr spectrum and tlc behavior shows that this material is contaminated with a significant amount of the starting steriod which is not readily separable from the more polar isomer of the product under the tlc systems examined. Partial separation of the two 17-isomers is achieved under these tlc conditions.

Workup

  1. distillationdistilled boron trifluoride etherate (0.3 ml)
  2. additionis added
  3. additionThe mixture is then diluted with dichloromethane
  4. washwashed successively with a saturated sodium bicarbonate solution and brine
  5. dry with materialdried (MgSO4 anh.)
  6. customis evaporated
  7. customto afford the crude title compound
  8. customThis material is chromatographed over a column of silica gel (20 g)
  9. washeluting the column with chloroform-hexane mixtures (1:1, 1:4), chloroform and chloroform-ethyl acetate (95:5)

Sources & evidence

ORD record
ord-56b917da08f145f2900b85bd392c369a
Source dataset
uspto-grants-1982_11
Patent number
US04361559

Reaction notes

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