Acetamidomalonic acid diethyl ester → HCID 86637846, compound

HRID 1399492Notes

Reaction equation

HRID 1399492 reaction equation
[Na].[C:2]([NH:5][CH:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:4])[CH3:3].[N:17]([CH2:20][CH2:21][CH2:22][CH2:23]Br)=[N+:18]=[N-:19]>CCO>[C:2]([NH:5][C:6]([CH2:23][CH2:22][CH2:21][CH2:20][N:17]=[N+:18]=[N-:19])([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:4])[CH3:3]

Participants

5

Reactant 3

HCID 14041Acetamidomalonic acid diethyl esterHCID 5360545SodiumHCID 13861950HCID 13861950, compound

Product 1

HCID 86637846HCID 86637846, compoundYield 63%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 0.598 g (0.026 mol) sodium metal in 25 ml absolute EtOH, 5.65 g diethyl acetamidomalonate (0.026 mol) was added, following previously published procedures (Chenault, H. K. et al., 1989). The mixture was stirred for 30 min at room temperature. By dropwise addition, azidobutylbromide 1a (4.82 g, 0.027 mol) was added with stirring. The reaction mixture was stirred for 2 h at room temperature and refluxed for 6 h at 80° C. After cooling overnight, the reaction mixture was concentrated to dryness, and the residue was extracted with diethyl ether. The combined ether extracts were washed with water, sat. NaHCO3, water, and brine, and were dried over MgSO4 and then concentrated. Silica gel chromatography (Hex:EtOAc=1:1) gave a product (63%) as a clear, viscous oil. 1H NMR (300 MHz, CDCl3): δ 6.77 (1H, s), 4.24 (4H, q, J=6.9 Hz), 3.26 (2H, t, J=6.9 Hz), 2.31-2.37 (2H, m), 2.04 (3H, s), 1.59 (2H, p, J=7.5 Hz), 1.26 (6H, t, J=6 Hz), 1.16-1.27 (2H, m). ESI-MS m/e 315.

Workup

  1. additionwas added
  2. stirringwith stirring
  3. stirringThe reaction mixture was stirred for 2 h at room temperature
  4. temperaturerefluxed for 6 h at 80° C
  5. temperatureAfter cooling overnight
  6. concentrationthe reaction mixture was concentrated to dryness
  7. extractionthe residue was extracted with diethyl ether
  8. washThe combined ether extracts were washed with water, sat. NaHCO3, water, and brine
  9. dry with materialwere dried over MgSO4
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-f86496c6085640c3b869b2f3ae5f8358
Source dataset
uspto-grants-2014_12
Patent number
US08906830B2

Reaction notes

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