Diethyl Oxalate → Ethyl 4-[2,4-bis(methoxymethoxy)-6-(4-nitrophenoxy)phenyl]-2,4-dioxobutanoate

HRID 880359Notes

Reaction equation

HRID 880359 reaction equation
CC(C)([O-])C.[Na+].[C:7]([O:14][CH2:15][CH3:16])(=[O:13])[C:8]([O:10]CC)=O.[CH3:17][O:18][CH2:19][O:20][C:21]1[CH:26]=[C:25]([O:27][CH2:28][O:29][CH3:30])[CH:24]=[C:23]([O:31][C:32]2[CH:37]=[CH:36][C:35]([N+:38]([O-:40])=[O:39])=[CH:34][CH:33]=2)[C:22]=1[C:41](=[O:43])[CH3:42]>C1COCC1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>[CH3:17][O:18][CH2:19][O:20][C:21]1[CH:26]=[C:25]([O:27][CH2:28][O:29][CH3:30])[CH:24]=[C:23]([O:31][C:32]2[CH:37]=[CH:36][C:35]([N+:38]([O-:40])=[O:39])=[CH:34][CH:33]=2)[C:22]=1[C:41](=[O:43])[CH2:42][C:8](=[O:10])[C:7]([O:14][CH2:15][CH3:16])=[O:13]

Participants

6

Reactant 3

HCID 7268Diethyl OxalateHCID 23676156Sodium t-butoxideHCID 667593101-[2,4-Bis(methoxymethoxy)-6-(4-nitrophenoxy)phenyl]ethanone

Product 1

HCID 66760003Ethyl 4-[2,4-bis(methoxymethoxy)-6-(4-nitrophenoxy)phenyl]-2,4-dioxobutanoateYield 81%

Reagents, catalysts & solvents 2

HCID 311Citric AcidSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of sodium tert-butoxide (31.5 g, 328 mmol) and diethyl oxalate (60.5 mL, 3 eq.) in THF (250 mL) was slowly added dropwise a solution of 1-[2,4-bis(methoxymethoxy)-6-(4-nitrophenoxy)phenyl]ethanone (56 g, 149 mmol) in THF (350 mL) at −5° C. After stirring for 1 hour at this temperature, the resulting solution was stirred for further 3 hours at room temperature. The solution was then taken up in 10% citric acid solution (2000 mL) and thoroughly extracted with ethyl acetate. After washing with brine and drying over Na2SO4, the solvent was removed to provide a yellowish residue that was taken up in light petrol ether to remove the excess of diethyl oxalate to afford the quite pure title compound (58 g, 81% yield).

Workup

  1. stirringthe resulting solution was stirred for further 3 hours at room temperature
  2. extractionthoroughly extracted with ethyl acetate
  3. washAfter washing with brine
  4. dry with materialdrying over Na2SO4
  5. customthe solvent was removed
  6. customto provide a yellowish residue that
  7. customto remove the excess of diethyl oxalate

Sources & evidence

ORD record
ord-9ef7c316c7cb4e04a80f2b8b8d766ecb
Source dataset
uspto-grants-2015_03
Patent number
US08993556B2

Reaction notes

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