Diethyl Oxalate → HCID 596592, compound

HRID 920713Notes

Reaction equation

HRID 920713 reaction equation
[O-]CC.[Na+].[C:5]([O:12][CH2:13][CH3:14])(=[O:11])[C:6]([O:8]CC)=O.[F:15][C:16]1[CH:17]=[C:18]([C:22](=[O:24])[CH3:23])[CH:19]=[CH:20][CH:21]=1>C(O)C>[F:15][C:16]1[CH:17]=[C:18]([C:22](=[O:24])[CH2:23][C:6](=[O:8])[C:5]([O:12][CH2:13][CH3:14])=[O:11])[CH:19]=[CH:20][CH:21]=1

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 99673-FluoroacetophenoneHCID 2723922Sodium ethoxide

Product 1

HCID 596592HCID 596592, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

To a solution of sodium ethoxide (123 g, 362 mmol) in ethanol (300 mL) at 0° C. was added a solution of diethyl oxalate (49.4 mL, 362 mmol) in ethanol (25 mL) and the resulting solution was stirred for 10 min. 1-(3-Fluorophenyl)ethanone (50 g, 362 mmol) in ethanol (25 mL) was added and the reaction mixture was stirred at room temperature for 16 h. Ethanol was distilled off under reduced pressure and the residue obtained was quenched with ice cold water and the brown product was filtered. This crude product was purified by ISCO using 220 g silica gel column and 20% ethyl acetate in hexane as eluent. The combined fractions were concentrated to afford Intermediate 4A (62.5 g, 73%). MS(ES): m/z=239 [M+H]+; 1H NMR (400 MHz, CDCl3) δ ppm 15.13 (bs, 1H), 7.77-7.83 (m, 1H), 7.67-7.73 (m, 1H), 7.51 (td, J=8.03, 5.48 Hz, 1H), 7.29-7.37 (m, 1H), 7.28 (s, 1H), 4.43 (q, J=7.18 Hz, 2H), 1.40-1.47 (m, 3H).

Workup

  1. stirringthe reaction mixture was stirred at room temperature for 16 h
  2. distillationEthanol was distilled off under reduced pressure
  3. customthe residue obtained
  4. customwas quenched with ice cold water
  5. filtrationthe brown product was filtered
  6. customThis crude product was purified by ISCO
  7. concentrationThe combined fractions were concentrated

Sources & evidence

ORD record
ord-b6244f6e4955454eb5e97f9cacdd7f58
Source dataset
uspto-grants-2016_03
Patent number
US09273058B2

Reaction notes

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