Diethyl Oxalate → Methyl 4-(4-methylphenyl)-2,4-dioxobutanoate

HRID 514392Notes

Reaction equation

HRID 514392 reaction equation
[Na].C(O[C:5](=[O:11])[C:6]([O:8][CH2:9]C)=[O:7])C.[CH3:12][C:13]1[CH:18]=[CH:17][C:16]([C:19](=[O:21])[CH3:20])=[CH:15][CH:14]=1>CO.CC(OC)(C)C>[CH3:12][C:13]1[CH:18]=[CH:17][C:16]([C:19](=[O:21])[CH2:20][C:5](=[O:11])[C:6]([O:8][CH3:9])=[O:7])=[CH:15][CH:14]=1

Participants

6

Reactant 3

HCID 7268Diethyl OxalateHCID 8500p-METHYLACETOPHENONEHCID 5360545Sodium

Product 1

HCID 308119Methyl 4-(4-methylphenyl)-2,4-dioxobutanoateYield 48.5%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 15413tert-Butyl methyl etherSolvent2×

Procedure

Sodium (1.0 g, 43 mmol) was dissolved in MeOH (50 mL) and then evaporated to a dry white powder. To the powder was added MTBE (100 mL) and diethyloxalate (5.14 g, 35.2 mmol). To the resulting solution was added a solution of 1-(4-methylphenyl)ethanone (5.0 g, 37.3 mmol) in MTBE (50 mL) dropwise over 45 min. The resulting suspension was allowed to stir for 1 h, and the precipitate was filtered and washed with MTBE/hexanes (1:1, 50 mL). The solid was suspended in 1 N HCl (100 mL) and extracted with EtOAc (2×100 mL). The combined extracts were dried (MgSO4), filtered, and concentrated to an oily residue which crystallized on standing at rt. The yellow solid was triturated with MTBE/hexanes (1:1) and filtered to give the title compound (3.76 g, 46%) as a white solid.

Workup

  1. customevaporated to a dry white powder
  2. filtrationthe precipitate was filtered
  3. washwashed with MTBE/hexanes (1:1, 50 mL)
  4. extractionextracted with EtOAc (2×100 mL)
  5. dry with materialThe combined extracts were dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated to an oily residue which
  8. customcrystallized
  9. customon standing at rt
  10. customThe yellow solid was triturated with MTBE/hexanes (1:1)
  11. filtrationfiltered

Sources & evidence

ORD record
ord-16e28af0ac0544e6abbfd64bae0bfbac
Source dataset
uspto-grants-2015_08
Patent number
US09107916B2

Reaction notes

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