Diethyl Oxalate → HCID 86682306, compound

HRID 1055208Notes

Reaction equation

HRID 1055208 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.CCCCCC.[CH3:19][N:20]([CH3:24])[C:21](=[O:23])[CH3:22].[C:25](OCC)(=[O:31])[C:26]([O:28][CH2:29][CH3:30])=[O:27]>C1COCC1>[CH3:19][N:20]([CH3:24])[C:21](=[O:23])[CH2:22][C:25](=[O:31])[C:26]([O:28][CH2:29][CH3:30])=[O:27]

Participants

7

Reactant 5

HCID 7268Diethyl OxalateHCID 7912DiisopropylamineHCID 8058HexaneHCID 31374DimethylacetamideHCID 178418339Butyllithium

Product 1

HCID 86682306HCID 86682306, compoundYield 29.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

10.2 g of diisopropylamine (0.1 mol) were dissolved in 100 ml of dry THF under nitrogen and cooled in a freezing mixture. 40 ml n-butyllithium in hexane (2.5 M, 0.1 mol) were slowly added dropwise. When the addition was completed it was allowed to stir for 60 minutes and then 8.7 g N,N-dimethylacetamide (0.1 mol) were added dropwise. The reaction mixture was stirred for another 20 min in the freezing mixture. In a second flask, 43.7 g of diethyl oxalate (0.3 mol) in 50 ml of dry THF were cooled in a freezing mixture and the cooled reaction mixture was cannulated with stirring in small portions to it. It was left overnight under stirring to warm to room temperature. The THF was removed on a rotary evaporator and the residue was taken up in 80 ml half concentrated hydrochloric acid. The aqueous phase was extracted five times with 150 ml ethyl acetate, the combined organic phases dried over sodium sulfate and concentrated on a rotary evaporator to dryness. The excess diethyl oxalate was removed by distillation (2-3 mbar, 80° C.) and 17 g of crude product were obtained. 5.5 g product was obtained as white crystals with a melting point of 28° C. after crystallization from n-hexane.

Workup

  1. temperaturecooled in a freezing mixture
  2. additionWhen the addition
  3. stirringThe reaction mixture was stirred for another 20 min in the freezing mixture
  4. customthe cooled reaction mixture
  5. stirringwith stirring in small portions to it
  6. waitIt was left overnight
  7. stirringunder stirring
  8. customThe THF was removed on a rotary evaporator
  9. extractionThe aqueous phase was extracted five times with 150 ml ethyl acetate
  10. dry with materialthe combined organic phases dried over sodium sulfate
  11. concentrationconcentrated on a rotary evaporator to dryness
  12. customThe excess diethyl oxalate was removed by distillation (2-3 mbar, 80° C.)
  13. custom17 g of crude product were obtained

Sources & evidence

ORD record
ord-898f73cfd6344fd4a7efa38d8a24e2a8
Source dataset
uspto-grants-2016_07
Patent number
US09394324B2

Reaction notes

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