Tert-butyl acetoacetate → 1-(Phenylthio)pentane-2,4-dione

HRID 1013101Notes

Reaction equation

HRID 1013101 reaction equation
[C:1]([CH:4]([C:12](=[O:21])[CH2:13][S:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)C(OC(C)(C)C)=O)(=[O:3])[CH3:2].C(OC(C)(C)C)(=O)CC(C)=O.CC(C)([O-])C.[Na+].C1(SCC(Cl)=O)C=CC=CC=1>C(OCC)C>[C:15]1([S:14][CH2:13][C:12](=[O:21])[CH2:4][C:1](=[O:3])[CH3:2])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

6

Reactant 4

HCID 15538Tert-butyl acetoacetateHCID 4063350(Phenylthio)acetyl chlorideHCID 23676156Sodium t-butoxideHCID 574477431,1-Dimethylethyl 2-acetyl-3-oxo-4-(phenylthio)butanoate

Product 1

HCID 125296471-(Phenylthio)pentane-2,4-dioneYield 48%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

1,1-Dimethylethyl 2-acetyl-3-oxo-4-(phenylthio)butanoate Add tert-butyl acetoacetate (1.30 mL, 8.0 mmol) dropwise to a solution of sodium tert-butoxide (770 mg, 8.0 mmol) in diethyl ether (15 mL) at 0° C. under nitrogen. Stir the white precipitate at RT for 20 h and cool to 0° C. Add (phenylthio)acetyl chloride (1.2 mL, 8.0 mmol) dropwise and observe as the suspension turns yellow, then becomes a clear solution, and finally forms a white precipitate when all the reagent is added. Stir the reaction for 24 h at RT. Quench with 2 N HCl (15 mL), wash the aqueous layer with EtOAc (15 mL). Dry (MgSO4), concentrate and purify (silica gel chromatography, eluting with 100:0 to 90:10 2-methylpentane:EtOAc) to give the title compound as light yellow solid (1.11 g, 48%)

Workup

  1. temperaturecool to 0° C
  2. additionis added
  3. stirringStir
  4. customthe reaction for 24 h at RT
  5. customQuench with 2 N HCl (15 mL)
  6. washwash the aqueous layer with EtOAc (15 mL)
  7. dry with materialDry (MgSO4)
  8. concentrationconcentrate
  9. custompurify
  10. wash(silica gel chromatography, eluting with 100:0 to 90:10 2-methylpentane:EtOAc)

Sources & evidence

ORD record
ord-c9b7a793ef7849aa9bb459c2313becd1
Source dataset
uspto-grants-2011_07
Patent number
US07981882B2

Reaction notes

Loading…