Acetic Acid → HCID 178468923, compound

HRID 895821Notes

Reaction equation

HRID 895821 reaction equation
[O-]CC.[Na+].[C:5]([O:12][CH2:13][CH3:14])(=[O:11])[C:6](OCC)=O.[CH3:15][C:16](=O)[CH2:17][CH3:18].C(O)(=O)C.O.[NH2:25][NH2:26]>C(O)C>[CH2:17]([C:16]1[CH:15]=[C:6]([C:5]([O:12][CH2:13][CH3:14])=[O:11])[NH:26][N:25]=1)[CH3:18]

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 6569Methyl Ethyl KetoneHCID 7268Diethyl OxalateHCID 24654Hydrazine hydrate (1:1)HCID 2723922Sodium ethoxide

Product 1

HCID 178468923HCID 178468923, compoundYield 89.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Ethanolic sodium ethoxide solution (21% w/w; 143 ml, 0.39 mol) was added dropwise to a stirred, ice-cooled solution of diethyl oxalate (59.8 ml, 0.44 mol) in absolute ethanol (200 ml) under nitrogen and the resulting solution stirred for 15 minutes. Butan-2-one (39 ml, 0.44 mol) was then added dropwise, the cooling bath removed, the reaction mixture stirred for 18 hours at room temperature and then for 6 hours at 40° C., then the cooling bath reintroduced. Next, glacial acetic acid (25 ml, 0.44 mol) was added dropwise, the resulting solution stirred for 30 minutes at 0° C., hydrazine hydrate (20 ml, 0.44 mol) added dropwise, then the reaction mixture allowed to warm to room temperature and maintained there over a period of 18 hours, before being evaporated under reduced pressure. The residue was partitioned between dichloromethane (300 ml) and water (100 ml), then the organic phase separated, washed with water (2×100 ml), dried (Na2SO4) and concentrated under reduced pressure to give the title compound (66.0 g). δ (CDCl3): 1.04 (3H, t), 1.16 (3H, t), 2.70 (2H, q), 4.36 (2H, q), 6.60 (1H, s). LRMS: m/z 169 (M+1)+.

Workup

  1. customthe cooling bath removed
  2. stirringthe reaction mixture stirred for 18 hours at room temperature
  3. waitfor 6 hours at 40° C.
  4. additionthe cooling bath reintroduced
  5. stirringthe resulting solution stirred for 30 minutes at 0° C.
  6. temperaturemaintained there over a period of 18 hours
  7. custombefore being evaporated under reduced pressure
  8. customThe residue was partitioned between dichloromethane (300 ml) and water (100 ml)
  9. customthe organic phase separated
  10. washwashed with water (2×100 ml)
  11. dry with materialdried (Na2SO4)
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-91ba6b5f1b4140b1a39830bc9e144785
Source dataset
uspto-grants-2005_07
Patent number
US06916927B2

Reaction notes

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