Diethyl Oxalate → HCID 57435094, compound

HRID 1366908Notes

Reaction equation

HRID 1366908 reaction equation
[H-].[Na+].[CH3:3][C:4]1([CH3:16])[CH2:9][CH2:8][CH2:7][CH:6]([CH3:10])[CH:5]1[CH2:11][CH2:12][C:13](=[O:15])[CH3:14].[CH2:17]([O:19][C:20](=[O:26])[C:21](OCC)=[O:22])[CH3:18].CC[O-].[Na+]>CCO>[CH2:17]([O:19][C:20](=[O:26])[C:21](=[O:22])[CH2:14][C:13](=[O:15])[CH2:12][CH2:11][CH:5]1[CH:6]([CH3:10])[CH2:7][CH2:8][CH2:9][C:4]1([CH3:3])[CH3:16])[CH3:18]

Participants

6

Reactant 4

HCID 7268Diethyl OxalateHCID 24758Sodium hydrideHCID 1107874-(2,2,6-TRIMETHYLCYCLOHEXYL)-2-BUTANONEHCID 2723922Sodium ethoxide

Product 1

HCID 57435094HCID 57435094, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Sodium hydride (0.6447 g, 25.52 mmol) was added slowly to a NaCl ice bath containing EtOH (10 mL, 2.6 M) stirring under N2. 4-(2,2,6-trimethylcyclohexyl)-butan-2-one (5.0072 g, 25.50 mmol) and diethyloxalate (3.7241 g, 25.48 mmol) were mixed together, and then added to the chilled NaOEt solution. After stirring for 5 minutes, the reaction was warmed to room temperature. The reaction quickly solidified. An additional 10 mL EtOH was added, and the reaction was allowed to stand for another 3 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, 1:1 Hexanes:CH2Cl2): Only pure fractions were combined and concentrated to obtain 52. 1H (CDCl3, 400 MHz): δ 14.51 (1H, broad s), 6.34 (1H, s), 4.34 (2H, q, J=7.1 Hz), 2.44 (2H, t, J=8.3 Hz), 1.96-1.84 (1H, m), 1.68-1.22 (m), 1.36 (3H, t, J=7.1 Hz), 1.18-0.98 (m), 0.94 (3H, s), 0.87 (3H, s), 0.85 (3H, d, J=7.3 Hz) ppm. Partial 13C (CDCl3, 100 MHz): δ 203.45, 167.17, 162.40, 101.80, 62.71, 49.28, 42.60, 30.46, 20.86, 14.27 ppm. Partial DEPT (CDCl3, 100 MHz): CH3 carbons: 14.27; CH2 carbons: 62.71; CH carbons: 101.80 ppm. HPLC: 12.576 min.

Workup

  1. stirringAfter stirring for 5 minutes
  2. customThe reaction
  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, 1:1 Hexanes:CH2Cl2)
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-be0eec3430b044e59ebcfca6b1bf5f7b
Source dataset
uspto-grants-2011_02
Patent number
US07893098B2

Reaction notes

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