Diethyl Oxalate → HCID 67400374, compound

HRID 1055206Notes

Reaction equation

HRID 1055206 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.CCCCCC.[CH3:19][N:20]1[CH2:25][CH2:24][CH2:23][CH2:22][C:21]1=[O:26].[C:27](OCC)(=[O:33])[C:28]([O:30][CH2:31][CH3:32])=[O:29]>C1COCC1>[CH3:19][N:20]1[CH2:25][CH2:24][CH2:23][CH:22]([C:27](=[O:33])[C:28]([O:30][CH2:31][CH3:32])=[O:29])[C:21]1=[O:26]

Participants

7

Reactant 5

HCID 7268Diethyl OxalateHCID 7912DiisopropylamineHCID 8058HexaneHCID 13603N-Methyl-2-piperidoneHCID 178418339Butyllithium

Product 1

HCID 67400374HCID 67400374, compoundYield 24.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

20.4 g of diisopropylamine (0.1 mol) were dissolved in 200 ml of dry THF under nitrogen and cooled in a freezing mixture. 80 ml n-butyllithium in hexane (2.5 M, 0.2 mol) were added dropwise slowly. After the addition it was allowed to stir for 60 minutes and then 22.6 g N-methyl-2-piperidone (0.2 mol) were added dropwise. The reaction mixture was stirred for another 20 min in the freezing mixture. In a second flask, 87.7 g diethyl oxalate (0.6 mol) in 100 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 300 ml ethyl acetate, the combined organic phases were 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 45 g of crude product were obtained. 10.4 g product was obtained as white crystals with a melting point of 23° C. after crystallization from diethyl ether/n-hexane.

Workup

  1. temperaturecooled in a freezing mixture
  2. additionAfter the addition it
  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 300 ml ethyl acetate
  10. dry with materialthe combined organic phases were 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. custom45 g of crude product were obtained

Sources & evidence

ORD record
ord-133e8bb1f5514a9ea1917080f51cba04
Source dataset
uspto-grants-2016_07
Patent number
US09394324B2

Reaction notes

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