Diethyl Oxalate → HCID 18408485, compound

HRID 993024Notes

Reaction equation

HRID 993024 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:13](=[O:15])[CH3:14])[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10].C([Li])CCC.[C:21](OCC)(=O)[C:22]([O:24][CH2:25][CH3:26])=[O:23].[Cl-].[NH4+:32].Cl.NO>C(O)C.CCCCCC>[CH3:12][O:11][C:7]1[CH:6]=[C:5]([C:13]2[O:15][N:32]=[C:21]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH:14]=2)[CH:4]=[C:3]([O:2][CH3:1])[C:8]=1[O:9][CH3:10]

Participants

8

Reactant 5

HCID 7268Diethyl OxalateHCID 143453',4',5'-TrimethoxyacetophenoneHCID 25517Ammonium ChlorideHCID 443297Hydroxyamine hydrochlorideHCID 178418339Butyllithium

Product 1

HCID 18408485HCID 18408485, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8058HexaneSolvent

Procedure

3′,4′,5′-Trimethoxyacetophenone (98%, 10.89 g) was suspended at −78° C. under an argon atmosphere, and a hexane solution (31.9 mL) of 1.59 M n-butyllithium was slowly added dropwise to the suspension. After 10 minutes, the suspension became homogeneous. Diethyl oxalate (8.16 g) was added dropwise to the homogeneous suspension, and the resultant mixture was stirred at the same temperature for 1 hour. A saturated aqueous solution (5 mL) of ammonium chloride was added to the reaction mixture and warmed to room temperature to conduct extraction with ethyl acetate. The resultant organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a yellow oil. The yellow oil was dissolved in ethanol (100 mL), and to the solution an aqueous solution (10 mL) of hydroxylamine hydrochloride (3.52 g), and the resultant mixture was refluxed for 1 hour. After the reaction mixture was concentrated under reduced pressure, the residue was diluted with ethyl acetate, washed with water and saturated brine and dried over anhydrous sodium sulfate. After the diluted residue was concentrated under reduced pressure, the residue was purified by column chromatography on silica gel (hexane:ethyl acetate=3:1) to obtain the title compound.

Workup

  1. customwas suspended at −78° C. under an argon atmosphere
  2. extractionextraction with ethyl acetate
  3. washThe resultant organic layer was washed with saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customto obtain a yellow oil
  7. concentrationAfter the reaction mixture was concentrated under reduced pressure
  8. additionthe residue was diluted with ethyl acetate
  9. washwashed with water and saturated brine
  10. dry with materialdried over anhydrous sodium sulfate
  11. concentrationAfter the diluted residue was concentrated under reduced pressure
  12. customthe residue was purified by column chromatography on silica gel (hexane:ethyl acetate=3:1)

Sources & evidence

ORD record
ord-a32480ea67924f119e9a8fab3fb8c2bb
Source dataset
uspto-grants-2002_10
Patent number
US06472386B1

Reaction notes

Loading…