Carbon Dioxide → 2,5-Bis[(tetrahydropyran-2-yl)oxymethyl]benzoic acid

HRID 1766853Notes

Reaction equation

HRID 1766853 reaction equation
C([Li])CCC.Br[C:7]1[CH:12]=[C:11]([CH2:13][O:14][CH:15]2[CH2:20][CH2:19][CH2:18][CH2:17][O:16]2)[CH:10]=[CH:9][C:8]=1[CH2:21][O:22][CH:23]1[CH2:28][CH2:27][CH2:26][CH2:25][O:24]1.[C:29](=[O:31])=[O:30].[Cl-].[NH4+]>O1CCCC1.CCCCCC.C(OCC)(=O)C>[O:24]1[CH2:25][CH2:26][CH2:27][CH2:28][CH:23]1[O:22][CH2:21][C:8]1[CH:9]=[CH:10][C:11]([CH2:13][O:14][CH:15]2[CH2:20][CH2:19][CH2:18][CH2:17][O:16]2)=[CH:12][C:7]=1[C:29]([OH:31])=[O:30]

Participants

8

Reactant 4

HCID 280Carbon DioxideHCID 25517Ammonium ChlorideHCID 211104512-Bromo-1,4-bis[(tetrahydropyran-2-yl)oxymethyl]benzeneHCID 178418339Butyllithium

Product 1

HCID 211104372,5-Bis[(tetrahydropyran-2-yl)oxymethyl]benzoic acidYield 50%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

n-Butyllithium (1.57 M hexane solution; 8.33 ml, 13.1 mmol) was added dropwise to a solution of 2-bromo-1,4-bis[(tetrahydropyran-2-yl)oxymethyl]benzene (3.55 g, 9.22 mmol) obtained from Example 1-(2) in tetrahydrofuran (30 ml) with stirring at −78° C. After the mixture was stirred at the same temperature for 20 minutes, carbon dioxide gas was introduced thereto for 40 minutes. The resulting mixture was stirred at the same temperature for 1 hour, and then the reaction was stopped by addition of a saturated aqueous solution of ammonium chloride. The mixture was warmed to 0° C., and then the product was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride, and the solvent was distilled off under reduced pressure to afford the residue. The residue was subjected to chromatography on a silica gel (100 g) column (eluent; ethyl acetate:hexane=1:3) to give the title compound (1.63 g, 50% yield) as a colorless oil.

Workup

  1. stirringAfter the mixture was stirred at the same temperature for 20 minutes
  2. stirringThe resulting mixture was stirred at the same temperature for 1 hour
  3. temperatureThe mixture was warmed to 0° C.
  4. extractionthe product was extracted with ethyl acetate
  5. washThe organic layer was washed with a saturated aqueous solution of sodium chloride
  6. distillationthe solvent was distilled off under reduced pressure
  7. customto afford the residue

Sources & evidence

ORD record
ord-cbea3d04070e40bda3839db7f1e42926
Source dataset
uspto-grants-2007_06
Patent number
US07230023B2

Reaction notes

Loading…