Diethyl Oxalate → HCID 57435097, compound

HRID 1366916Notes

Reaction equation

HRID 1366916 reaction equation
[H-].[Na+].[CH3:3][CH:4]([CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[C:5](=[O:7])[CH3:6].[CH2:15]([O:17][C:18](=[O:24])[C:19](OCC)=[O:20])[CH3:16].CC[O-].[Na+]>CCO>[CH2:15]([O:17][C:18](=[O:24])[C:19](=[O:20])[CH2:6][C:5](=[O:7])[CH:4]([CH3:3])[CH2:8][C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1)[CH3:16]

Participants

6

Reactant 4

HCID 7268Diethyl OxalateHCID 24758Sodium hydrideHCID 1028472-Butanone, 3-methyl-4-phenyl-HCID 2723922Sodium ethoxide

Product 1

HCID 57435097HCID 57435097, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Sodium hydride (0.3965 g, 16.52 mmol) was added slowly to a NaCl ice bath containing EtOH (5.6 mL, 2.6 M) stirring under N2. 59 (2.2727 g, 14.01 mmol) and diethyloxalate (2.0649 g, 14.13 mmol) were mixed together, and then added to the chilled NaOEt solution. After stirring for 5 minutes, the reaction was warmed to room temperature. After stirring for 5 h, 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, concentrated, and purified by silica gel chromatography (Combiflash column, 67:30:3 Hexanes:CH2Cl2:2N NH3 in EtOH): Only pure fractions were combined and concentrated to obtain 60. 1H (CDCl3, 400 MHz): δ 14.55 (1H, broad s), 7.32-7.12 (5H, m), 6.36 (1H, s), 4.33 (2H, q, J=7.0 Hz), 3.05 (1H, dd, J=13.5, 6.8 Hz), 2.84 (1H, app sex, J=7.0 Hz), 2.67 (1H, dd, J=13.5, 7.8 Hz), 1.36 (3H, t, J=7.1 Hz), 2.33 (3H, d, J=7.0 Hz) ppm. 13C (CDCl3, 100 MHz): δ 205.78, 166.96, 161.88, 138.75, 128.80, 128.30, 126.29, 100.75, 62.32, 46.35, 39.10, 16.51, 13.88 ppm. DEPT (CDCl3, 100 MHz): CH3 carbons: 16.51, 13.88; CH2 carbons: 62.32, 39.10; CH carbons: 128.80, 128.30, 126.29, 100.75, 46.35 ppm. HPLC: 11.084 min.

Workup

  1. stirringAfter stirring for 5 minutes
  2. stirringAfter stirring for 5 h
  3. customthe reaction was quenched at 0° C. with 1N HCl
  4. extractionextracted 2× with CH2Cl2
  5. washThe combined organics were washed with H2O
  6. dry with materialdried with Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified by silica gel chromatography (Combiflash column, 67:30:3 Hexanes:CH2Cl2:2N NH3 in EtOH)
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-5b4f4278cbbe4628bc1de2d6be7a185c
Source dataset
uspto-grants-2011_02
Patent number
US07893098B2

Reaction notes

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