tert-Butyl bromoacetate → 1-Acetyl-3-benzylidene piperazine-2,5-dione N-butyl acetate

HRID 396871Notes

Reaction equation

HRID 396871 reaction equation
[C:1]([N:4]1[CH2:9][C:8](=[O:10])[NH:7][C:6](=[CH:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:5]1=[O:18])(=[O:3])[CH3:2].Br[CH2:20][C:21]([O:23][C:24]([CH3:27])(C)C)=[O:22]>CN(C=O)C.[Ag]=O>[C:1]([N:4]1[CH2:9][C:8](=[O:10])[NH:7][C:6](=[CH:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:5]1=[O:18])(=[O:3])[CH3:2].[CH3:1][CH2:2][CH2:27][CH2:24][O:23][C:21]([CH3:20])=[O:22]

Participants

5

Reactant 2

HCID 79177tert-Butyl bromoacetateHCID 37596531-Acetyl-3-benzylidene-2,5-piperazinedione

Product 1

HCID 1317240391-Acetyl-3-benzylidene piperazine-2,5-dione N-butyl acetateYield 114.6%

Reagents, catalysts & solvents 2

HCID 92152Silver(II) oxideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
45 °C

Procedure

To a solution containing 6.36. g (26.00 mmol) of 1-Acetyl-3-benzylidene piperazine-2,5-dione described by D. Villemn, et al. (Synthetic Communications, 20:3325 (1990)), in 100 mL of DMF under nitrogen atmosphere was added 9.62 mL (65.10 mmol) of t-butyl bromoacetate and 7.55 g (32.60 mmol) of silver oxide. The reaction was heated to 45° C. overnight. The reaction was filtered through a plug of celite and the filtrate concentration under reduced pressure. The residue was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 1% methanol/dichloromethane gave 5.37 g of a tan solid. Further purification via preparative HPLC gave 2.5 g (27%) of the title compound. FAB MS [M+H] m/z: Calcd: 359, Found: 359.

Workup

  1. additionTo a solution containing 6.36
  2. filtrationThe reaction was filtered through a plug of celite
  3. concentrationthe filtrate concentration under reduced pressure
  4. additionThe residue was diluted with ethyl acetate
  5. washwashed with water
  6. dry with materialThe organic phase was dried over magnesium sulfate
  7. filtrationFiltration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 1% methanol/dichloromethane

Sources & evidence

ORD record
ord-e8159846992f457fb8b36e2973cbebb9
Source dataset
uspto-grants-2003_08
Patent number
US06608175B2

Reaction notes

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