Acetone → (1,6-Dibromo-naphthalen-2-yloxy)-acetic acid ethyl ester

HRID 1373864Notes

Reaction equation

HRID 1373864 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[C:9](O)=[C:8]([Br:14])[CH:7]=[CH:6]2.[C:15](=[O:18])([O-])[O-:16].[Cs+].[Cs+].[Br:21]CC(OCC)=O.C[C:29]([CH3:31])=O>>[CH2:29]([O:16][C:15](=[O:18])[CH2:1][O:2][C:3]1[CH:12]=[CH:11][C:10]2[C:5](=[CH:6][CH:7]=[C:8]([Br:14])[CH:9]=2)[C:4]=1[Br:21])[CH3:31]

Participants

5

Reactant 4

HCID 180AcetoneHCID 7748Ethyl bromoacetateHCID 10796Cesium carbonateHCID 210759052-Bromo-6-methoxynaphthalen-1-ol

Product 1

HCID 981253(1,6-Dibromo-naphthalen-2-yloxy)-acetic acid ethyl esterYield 75.6%

Procedure

A mixture of 6-methoxy-2-bromonaphthol (20.1 g, 66.6 mmol) and cesium carbonate (43.2 g, 133 mmol) in acetone (200 mL) was stirred at ambient temperature for one hour. Ethyl bromoacetate (8.8 mL, 80 mmol) was then added. The reaction mixture was stirred for 23 hours at ambient temperature. The insoluble material was then filtered off, and the acetone filtrate was solvent evaporated. It was then partitioned in water and ethyl acetate. The organic phase was washed with water and brine. It was then dried with anhydrous magnesium sulfate, filtered and solvent evaporated. The resulting residue was stirred in hexane for 10 minutes, filtered and rinsed with hexane. It was then dried at 64° C. in vacuo for 25 hours to yield (1,6-dibromo-naphthalen-2-yloxy)-acetic acid ethyl ester as a light yellow solid (19.5 g, 75.6%): MP: 104–6° C.; mass spectrum (+EI, M+) m/z 388. 1H NMR (500 MHz, DMSO-d6): δ8.24 (d, 1H, J=1.99 Hz), 8.03 (d, 1H, J=9.01 Hz), 7.95 (d, 1H, J=9.01 Hz), 7.75 (dd, 1H, J=9.09 Hz and 2.07 Hz), 7.47 (d, 1H,J=9.17 Hz), 5.07 (s, 2H), 4.17 (q, 2H, J=7.07 Hz), 1.21 ppm (t, 3H, J=7.07 Hz). Elemental Analysis for C14H12Br2O3: Calcd: C, 43.33; H, 3.12; N, 0.00; Found: C, 43.40; H, 3.10; N, 0.00.

Workup

  1. stirringThe reaction mixture was stirred for 23 hours at ambient temperature
  2. filtrationThe insoluble material was then filtered off
  3. customevaporated
  4. customIt was then partitioned in water
  5. washThe organic phase was washed with water and brine
  6. dry with materialIt was then dried with anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customsolvent evaporated
  9. stirringThe resulting residue was stirred in hexane for 10 minutes
  10. filtrationfiltered
  11. washrinsed with hexane
  12. customIt was then dried at 64° C. in vacuo for 25 hours

Sources & evidence

ORD record
ord-075f771041d54b7b97c0ae963f0fdafc
Source dataset
uspto-grants-2007_01
Patent number
US07163954B2

Reaction notes

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