4-Hydroxybenzyl Alcohol → Acetic acid, [4-(hydroxymethyl)phenoxy]-, ethyl ester

HRID 1459433Notes

Reaction equation

HRID 1459433 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][OH:7])=[CH:4][CH:3]=1.C([O-])([O-])=O.[Cs+].[Cs+].Br[CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19]>CN(C=O)C>[OH:7][CH2:6][C:5]1[CH:8]=[CH:9][C:2]([O:1][CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:3][CH:4]=1

Participants

5

Reactant 3

HCID 1254-Hydroxybenzyl AlcoholHCID 7748Ethyl bromoacetateHCID 10796Cesium carbonate

Product 1

HCID 11413157Acetic acid, [4-(hydroxymethyl)phenoxy]-, ethyl esterYield 59%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a 500 mL round bottomed flask with a stirring bar and an argon inlet was added 4-hydroxybenzyl alcohol (7.50 g, 60.42 mmol), Cs2CO3 (29.53 g, 90.63 mmol), DMF (100 mL), and ethyl bromoacetate (11.09 g, 66.46 mmol). This mixture was stirred at ambient temperature for 2 h. The mixture was filtered and the filtrate was concentrated in vacuo. The residue was partitioned between EtOAc and water. The layers were separated and the organic phase was washed with two additional portions of water. Drying (MgSO4), filtration and removal of the solvent in vacuo, gave an oil. This material was chromatographed on 250 g of silica gel using 1:1 EtOAc-hexane as eluant. There was obtained ethyl 2-(4-hydroxymethyl-phenoxy)acetate 35-4 (7.47 g, 59%) as an oil. 1H NMR (CDCl3): δ 1.29 (t, J=7 Hz, 3H), 2.07 (br s, 1H), 4.26 (q, J=7 Hz, 2H), 4.58 (s, 2H), 4.60 (s, 2H), 6.88 (d, J=9 Hz, 2H), 7.27 (d, J=9 Hz, 2H).

Workup

  1. filtrationThe mixture was filtered
  2. concentrationthe filtrate was concentrated in vacuo
  3. customThe residue was partitioned between EtOAc and water
  4. customThe layers were separated
  5. washthe organic phase was washed with two additional portions of water
  6. customDrying
  7. filtration(MgSO4), filtration and removal of the solvent in vacuo
  8. customgave an oil
  9. customThis material was chromatographed on 250 g of silica gel using 1:1 EtOAc-hexane as eluant

Sources & evidence

ORD record
ord-1ea32c3b8aeb45d982843e20f0767ee5
Source dataset
uspto-grants-1998_12
Patent number
US05854245

Reaction notes

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