Diethyl Oxalate → HCID 89370582, compound

HRID 2280862Notes

Reaction equation

HRID 2280862 reaction equation
[Na].[CH2:2]=[C:3]1[CH2:6][CH:5]([C:7](=[O:9])[CH3:8])[CH2:4]1.[O-]CC.[Na+].[C:14](OCC)(=[O:20])[C:15]([O:17][CH2:18][CH3:19])=[O:16]>CCO>[CH2:2]=[C:3]1[CH2:6][CH:5]([C:7](=[O:9])[CH2:8][C:14](=[O:20])[C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH2:4]1

Participants

6

Reactant 4

HCID 7268Diethyl OxalateHCID 2723922Sodium ethoxideHCID 5360545SodiumHCID 45084997Ethanone, 1-(3-methylenecyclobutyl)- (9CI)

Product 1

HCID 89370582HCID 89370582, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Sodium (1.15 g, 49.9 mmol) was dissolved in dry EtOH (30 mL, denaturated with 5% diethylether). Compound 8a (5.5 g, 49.9 mmol, crude) was dissolved in dry EtOH (45 mL) and the above prepared sodium ethoxide solution was added. This mixture was stirred at rt for 15 min and then diethyl oxalate (6.8 mL, 49.9 mmol) was added dropwise. The reaction mixture was placed in a pre-heated (to 67° C.) oil bath and stirred at this temperature for 4.5 h. The mixture was left at rt overnight. The solvent was removed, EA (100 mL) and 1 M HCl (70 mL) were added and organic phase was separated. The aq. phase was re-extracted with EA (50 mL). The combined organic phases were washed with water, brine and dried over anh. Na2SO4. The solvent was removed under reduced pressure and the residue was purified on silica using hexanes/MTBE 9:1 as eluent giving pure product 8b. Yield: 6.29 g, 56% over two steps. 1H-NMR (CDCl3), δ (ppm): 6.36 (s, 1H), 4.85-4.80 (m, 2H), 4.34 (q, J=8.0 Hz, 2H), 3.35-3.25 (m, 1H), 3.05-2.85 (m, 4H), 1.36 (t, J=8.0 Hz, 3H).

Workup

  1. additionwas added
  2. temperaturea pre-heated (to 67° C.) oil bath
  3. stirringstirred at this temperature for 4.5 h
  4. waitThe mixture was left at rt overnight
  5. customThe solvent was removed
  6. additionEA (100 mL) and 1 M HCl (70 mL) were added
  7. customorganic phase was separated
  8. extractionThe aq. phase was re-extracted with EA (50 mL)
  9. washThe combined organic phases were washed with water, brine
  10. dry with materialdried over anh. Na2SO4
  11. customThe solvent was removed under reduced pressure
  12. customthe residue was purified on silica

Sources & evidence

ORD record
ord-79ba2ce61ecd40538ddd16aa0df027ac
Source dataset
uspto-grants-2015_09
Patent number
US09139539B2

Reaction notes

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