Gamma-Butyrolactone → Butanoic acid, 4-(phenylthio)-

HRID 1107135Notes

Reaction equation

HRID 1107135 reaction equation
[H-].[Na+].[C:3]1([SH:9])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[C:10]1(=[O:15])[O:14][CH2:13][CH2:12][CH2:11]1.[OH-].[Na+]>C1COCC1.O>[C:3]1([S:9][CH2:13][CH2:12][CH2:11][C:10]([OH:15])=[O:14])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

7

Reactant 4

HCID 7302Gamma-ButyrolactoneHCID 7969ThiophenolHCID 14798Sodium HydroxideHCID 24758Sodium hydride

Product 1

HCID 97324Butanoic acid, 4-(phenylthio)-Yield 81.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of sodium hydride (60% in mineral oil, 10.4 g, 0.26 mol) in anhydrous THF (400 mL) at ambient temperature is added thiophenol (26 g, 0.23 mol) dropwise via syringe. The resulting white suspension is stirred for 30 minutes under a nitrogen atmosphere then γ-butyrolactone (22.4 g, 0.26 mol) is added. The mixture is warmed to gentle reflux and stirred for 6 hours after which it became a solid mass and is allowed to cool to room temperature and stand overnight. The mixture is dissolved in water (1200 mL) containing 1 N NaOH (100 mL) and is extracted with diethyl ether (2×500 mL). The aqueous layer is acidified with 1N HCl and extracted with diethyl ether (3×500 mL). The organic extracts are washed with brine (300 mL) then dried over MgSO4, filtered and concentrated to afford a white solid which is chromatographed on silica gel (pet-ether/EtOAc, 19:1→9:1) to afford 4-phenylsulfanylbutanoic acid (36.6 g, 79%) as a white solid. TLC analysis [pet-ether/EtOAc, 1:1, Rf (thiophenol)=0.90, Rf (acid)=0.50]. m.p. 73-74° C.; 1H NMR (300 MHz, CDCl3) δ 1.95 (quint, J=7.1 Hz, 2H), 2.52 (t, J=7.2 Hz, 2H), 2.97 (t, J=7.1 Hz, 2H), 7.1-7.3 (m, 5H) ppm. Mass spectrum (EI) m/z 196 (M)+.

Workup

  1. temperatureThe mixture is warmed
  2. temperatureto gentle reflux
  3. stirringstirred for 6 hours after which it
  4. waitstand overnight
  5. extractionis extracted with diethyl ether (2×500 mL)
  6. extractionextracted with diethyl ether (3×500 mL)
  7. washThe organic extracts are washed with brine (300 mL)
  8. dry with materialthen dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customto afford a white solid which
  12. customis chromatographed on silica gel (pet-ether/EtOAc, 19:1→9:1)

Sources & evidence

ORD record
ord-271f5101b29b4626a7929756a154e125
Source dataset
uspto-grants-2000_05
Patent number
US06057369

Reaction notes

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