Dimethyl Carbonate → Dimethyl 2-(4-phenoxyphenyl)malonate

HRID 1386641Notes

Reaction equation

HRID 1386641 reaction equation
[H-].[Na+].[O:3]([C:10]1[CH:15]=[CH:14][C:13]([CH2:16][C:17]([O:19][CH3:20])=[O:18])=[CH:12][CH:11]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH3:21][O:22][C:23](=O)[O:24]C>C1COCC1>[O:3]([C:10]1[CH:11]=[CH:12][C:13]([CH:16]([C:23]([O:22][CH3:21])=[O:24])[C:17]([O:19][CH3:20])=[O:18])=[CH:14][CH:15]=1)[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1

Participants

5

Reactant 3

HCID 12021Dimethyl CarbonateHCID 24758Sodium hydrideHCID 12531834Methyl [p-(phenoxy)phenyl]acetate

Product 1

HCID 15540880Dimethyl 2-(4-phenoxyphenyl)malonateYield 76.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of NaH (1.02 g of 60% NaH in mineral oil washed with hexanes, 0.61 g, 25.6 mmol) in dry THF (30 mL) was added methyl (4-phenoxyphenyl)acetate (2.7 g, 11.1 mmol ) in dry THF (10 mL). The resulting mixture was stirred at room temperature for 30 minutes and then dimethylcarbonate (4.0 g, 3.75 mL, 44.4 mmol) was added . The reaction mixture was heated to reflux overnight and then cooled to room temperature, quenched with 1N HCl (60 mL), and extracted with ether (2×100 mL). The combined organic extracts were washed with water, then brine, dried (Na2SO4), concentrated, and purified using HPLC (porasil) eluted with 15% EtOAc/hexanes to give 2.56 g of dimethyl 2-(4-phenoxyphenyl)malonate as a white solid: 1H NMR (200 mHz, CDCl3) δ 7.39-6.92 (9H, m), 4.65 (1H, s), 3.75 (6H, s).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux overnight
  3. temperaturecooled to room temperature
  4. customquenched with 1N HCl (60 mL)
  5. extractionextracted with ether (2×100 mL)
  6. washThe combined organic extracts were washed with water
  7. dry with materialbrine, dried (Na2SO4)
  8. concentrationconcentrated
  9. custompurified
  10. washeluted with 15% EtOAc/hexanes

Sources & evidence

ORD record
ord-25a6cbcb2f6f4c4f92b12e3f6e0ac838
Source dataset
uspto-grants-2001_07
Patent number
US06265578B1

Reaction notes

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