Thiophenol → HCID 70400272, compound

HRID 371054Notes

Reaction equation

HRID 371054 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O.[C:32]([O:35][C@H:36]1[CH2:53][C@@:51]2([CH3:52])[C@@H:47]([CH2:48][CH2:49][C@@H:50]2O)[C@H:46]2[C@@:37]1([F:57])[C@:38]1([CH3:56])[C:43]([CH2:44][CH2:45]2)=[CH:42][C:41](=[O:55])[CH:40]=[CH:39]1)(=[O:34])[CH3:33].[C:58]1([SH:64])[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=1>O1CCCC1.C(OCC)(=O)C.C(Cl)(Cl)Cl>[C:32]([O:35][C@H:36]1[CH2:53][C@@:51]2([CH3:52])[C@@H:47]([CH2:48][CH2:49][C@H:50]2[S:64][C:58]2[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=2)[C@H:46]2[C@@:37]1([F:57])[C@:38]1([CH3:56])[C:43]([CH2:44][CH2:45]2)=[CH:42][C:41](=[O:55])[CH:40]=[CH:39]1)(=[O:34])[CH3:33]

Participants

8

Reactant 4

HCID 7969ThiophenolHCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 13421127HCID 13421127, compound

Product 1

HCID 70400272HCID 70400272, compound

Reagents, catalysts & solvents 3

HCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a magnetically stirred solution of triphenylphosphine (1.05 g) in dry tetrahydrofuran (15.0 ml) maintained at 0° C. was added diethylazodicarboxylate (0.488 ml) and the mixture was stirred at 0° C. for thirty minutes. To this stirred solution at 0° C. was added dropwise, a mixture of (11β,17β)-11-(acetyloxy)-9-fluoro-17-hydroxyandrosta-1,4-dien-3-one (362 mg, 1 mmole) and thiophenol (0.276 ml) dissolved in 5.0 ml of tetrahydrofuran. The solution was added over a ten minute period and then the reaction mixture stirred for 1 hour at 0° C., followed by 5.5 hours at room temperature. TLC (silica gel, 7:3 chloroform:ethyl acetate) indicated very little reaction taking place so the mixture was refluxed under nitrogen for 48.0 hours, followed by quenching in water and extraction with chloroform (4×50 ml). The combined chloroform extracts were dried over anhydrous magnesium sulfate and evaporated to a yellow oil. This was dissolved in a mixture of chloroform and hexane (8:2) and preadsorbed on silica gel. Flash chromatography was performed and the desired product was successfully eluted with (9:1) chloroform:hexane. The product-containing fractions were pooled, evaporated to an oil, taken up in hot ethyl acetate and evaporated to a yellow crystalline material which was vacuum dried.

Workup

  1. additionTo this stirred solution at 0° C. was added dropwise
  2. additionThe solution was added over a ten minute period
  3. stirringthe reaction mixture stirred for 1 hour at 0° C.
  4. customreaction
  5. temperaturewas refluxed under nitrogen for 48.0 hours
  6. customby quenching in water
  7. extractionextraction with chloroform (4×50 ml)
  8. dry with materialThe combined chloroform extracts were dried over anhydrous magnesium sulfate
  9. customevaporated to a yellow oil
  10. dissolutionThis was dissolved in a mixture of chloroform and hexane (8:2)
  11. washthe desired product was successfully eluted with (9:1) chloroform
  12. customevaporated to an oil
  13. customevaporated to a yellow crystalline material which
  14. customdried

Sources & evidence

ORD record
ord-6e4973e93844415a9b1728945e10e68c
Source dataset
uspto-grants-1985_07
Patent number
US04529548

Reaction notes

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