Diethyl Oxalate → 6-(4-Methoxyphenyl)-2,4-dioxohexanoic acid ethyl ester

HRID 1366885Notes

Reaction equation

HRID 1366885 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][C:11](=[O:13])[CH3:12])=[CH:5][CH:4]=1.[CH2:14]([O:16][C:17](=[O:23])[C:18](OCC)=[O:19])[CH3:15].CC[O-].[Na+]>CCO>[CH2:14]([O:16][C:17](=[O:23])[C:18](=[O:19])[CH2:12][C:11](=[O:13])[CH2:10][CH2:9][C:6]1[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=1)[CH3:15]

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 61007AnisylacetoneHCID 2723922Sodium ethoxide

Product 1

HCID 574350756-(4-Methoxyphenyl)-2,4-dioxohexanoic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

4-(4-methoxyphenyl)-2-butanone (14.9908 g, 84.2 mmol) and diethyloxalate (12.3434 g, 84.2 mmol) were mixed together, and then added to a solution of NaOEt (3 M, 28.1 mL) stirring in an ice bath under N2. After stirring for 15 minutes, the reaction was warmed to room temperature and stirred. After 10 min, the reaction completely solidified. An additional 100 mL EtOH was added, the reaction was placed on mechanical shaker overnight. The reaction was quenched at 0° C. with 1N HCl and extracted 2× with CH2Cl2. The combined organics were washed with H2O, dried with Na2SO4, filtered, and concentrated to yield crude 22. The crude material was purified with 1:1 Hexanes:CH2Cl2 to obtain 22. 1H (CDCl3, 400 MHz): δ 14.39 (1H, broad s), 7.10 (2H, d, J=7.1 Hz), 6.82 (2H, d, J=6.3 Hz), 6.34 (1H, s), 4.33 (2H, q, J=7.1 Hz), 3.77 (3H, s), 2.91 (2H, t, J=7.3 Hz), 2.78 (2H, t, J=7.3 Hz), 1.36 (3H, t, J=7.1 Hz) ppm. 13C (CDCl3, 100 MHz): δ 202.53, 166.46, 162.29, 158.36, 132.36, 129.44, 114.20, 102.11, 62.75, 55.47, 43.02, 29.94, 14.27 ppm. DEPT (CDCl3, 100 MHz): CH3 carbons: 55.47, 14.27; CH2 carbons: 62.75, 43.02, 29.94; CH carbons: 129.44, 114.20, 102.11 ppm. HPLC: 10.12 min. (Starting material: HPLC: 9.10 min.)

Workup

  1. stirringAfter stirring for 15 minutes
  2. stirringstirred
  3. customthe reaction
  4. customwas placed on mechanical shaker overnight
  5. customThe reaction was quenched at 0° C. with 1N HCl
  6. extractionextracted 2× with CH2Cl2
  7. washThe combined organics were washed with H2O
  8. dry with materialdried with Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customto yield crude 22
  12. customThe crude material was purified with 1:1 Hexanes

Sources & evidence

ORD record
ord-9be54dbdbdb640548885fa7312c79988
Source dataset
uspto-grants-2011_02
Patent number
US07893098B2

Reaction notes

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