Carbon Dioxide → 4-(2-Tetrahydropyranyloxyethoxy)benzoic acid

HRID 2198685Notes

Reaction equation

HRID 2198685 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][CH2:9][O:10][C:11]1[CH:16]=[CH:15][C:14](Br)=[CH:13][CH:12]=1.[Mg].[C:19](=[O:21])=[O:20]>O1CCCC1>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][CH2:9][O:10][C:11]1[CH:16]=[CH:15][C:14]([C:19]([OH:21])=[O:20])=[CH:13][CH:12]=1

Participants

5

Reactant 3

HCID 280Carbon DioxideHCID 5462224Magnesium2×HCID 128104732-[2-(4-Bromophenoxy)ethoxy]tetrahydro-2H-pyran

Product 1

HCID 128104744-(2-Tetrahydropyranyloxyethoxy)benzoic acid

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A mixture of 9.45 g (31.4 mmol) of 4-(2-tetrahydropyranyloxyethoxy)bromobenzene, 40 ml of dry tetrahydrofuran (THF) and 0.76 g (31.4 mmol) of magnesium metal is heated to boiling, and after about 15 minutes a spontaneous reaction ensues. The mixture is then maintained, with some external heating, at its boiling point and after 15 minutes 20 ml of THF is added. After an additional 15 minutes at boiling, a final 20 ml of THF is added, and boiling is continued until the total heating time is 2 hours. Most of the magnesium has disappeared at this point. The mixture is then cooled and carbon dioxide gas is introduced, at a slight positive pressure and with vigorous stirring, for 15 minutes. The mixture is filtered and rotoevaporated to remove the solvent. Ethyl acetate (150 ml), water (150 ml) and aqueous 3 N sulfuric acid (20 ml) are added to the residue. The aqueous layer is separated and extracted with ethyl acetate. The combined organic layers are washed with water (100 ml, 2X) and then with saturated aqueous sodium chloride and dried over calcium sulfate. Solvent is removed by rotoevaporation to give 4-(2-tetrahydropyranyloxyethoxy)benzoic acid.

Workup

  1. temperatureis heated
  2. customafter about 15 minutes a spontaneous reaction
  3. additionis added
  4. waitis 2 hours
  5. temperatureThe mixture is then cooled
  6. filtrationThe mixture is filtered
  7. customto remove the solvent
  8. additionEthyl acetate (150 ml), water (150 ml) and aqueous 3 N sulfuric acid (20 ml) are added to the residue
  9. customThe aqueous layer is separated
  10. extractionextracted with ethyl acetate
  11. washThe combined organic layers are washed with water (100 ml, 2X)
  12. dry with materialwith saturated aqueous sodium chloride and dried over calcium sulfate
  13. customSolvent is removed by rotoevaporation

Sources & evidence

ORD record
ord-71c447c50602479e812ee4e38490fb4f
Source dataset
uspto-grants-1982_11
Patent number
US04359424

Reaction notes

Loading…