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Hydrogen Sulfide → 17beta-Ethylthio-9-fluoro-11beta-hydroxy-17alpha-mercaptoandrosta-1,4-diene-3-one

HRID 1903000
Notes
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Reaction equation

HRID 1903000 reaction equation
[CH2:1]([S:3][C:4]1[C@:5]2([CH2:22][C@H:21]([OH:23])[C@@:20]3([F:24])[C@@H:10]([CH2:11][CH2:12][C:13]4[C@:18]3([CH3:19])[CH:17]=[CH:16][C:15](=[O:25])[CH:14]=4)[C@@H:7]2[CH2:8][CH:9]=1)[CH3:6])[CH3:2].[SH2:26].B(F)(F)F.CCOCC>ClCCl.C(Cl)(Cl)Cl>[CH3:2][CH2:1][S:3][C@@:4]1([SH:26])[CH2:9][CH2:8][C@H:7]2[C@H:10]3[C@:20]([F:24])([C@@H:21]([OH:23])[CH2:22][C@:5]12[CH3:6])[C@:18]1([CH3:19])[C:13](=[CH:14][C:15](=[O:25])[CH:16]=[CH:17]1)[CH2:12][CH2:11]3
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 402Hydrogen SulfideHCID 8000Boron trifluoride etherateHCID 1291771217-Ethylthio-9-fluoro-11beta-hydroxyandrosta-1,4,16-triene-3-one

Product 1

HCID 1327444317beta-Ethylthio-9-fluoro-11beta-hydroxy-17alpha-mercaptoandrosta-1,4-diene-3-one

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolvent
HCID 6344DichloromethaneSolvent

Conditions

Temperature
-40 °C

Procedure

A solution of 2.0 g of 17-ethylthio-9-fluoro-11β-hydroxyandrosta-1,4,16-triene-3-one in dry dichloromethane (120 ml) was cooled and stirred in a bath at about -40° C. and a slow stream of hydrogen sulfide gas was passed into the solution while boron trifluoride etherate (1.2 ml) was added. After about 3.5 to 4.0 hours, the mixture was diluted with chloroform, warmed to room temperature and washed successively with a dilute sodium bicarbonate solution and water. The solution was dried (anhydrous magnesium sulfate), evaporated and the solid residue crystallized from ethyl acetate to afford 1.4 g of the title compound, melting point 239°-242° C.

Workup

  1. additionwas added
  2. temperaturewarmed to room temperature
  3. washwashed successively with a dilute sodium bicarbonate solution and water
  4. dry with materialThe solution was dried (anhydrous magnesium sulfate)
  5. customevaporated
  6. customthe solid residue crystallized from ethyl acetate

Sources & evidence

ORD record
ord-9f6eb3123446479288bee69076f69062
Source dataset
uspto-grants-1984_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04435326

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes