1,3-Dibromobenzene → HCID 57475766, compound

HRID 1842265Notes

Reaction equation

HRID 1842265 reaction equation
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([Br:13])[CH:8]=1.[O:14]1[CH2:19][CH2:18][C:17](=O)[CH2:16][CH2:15]1.[Cl-].[NH4+]>O1CCCC1>[Br:13][C:9]1[CH:8]=[C:7]([C:17]2[CH2:18][CH2:19][O:14][CH2:15][CH:16]=2)[CH:12]=[CH:11][CH:10]=1

Participants

6

Reactant 4

HCID 79271,3-DibromobenzeneHCID 25517Ammonium ChlorideHCID 121599Tetrahydro-4H-pyran-4-oneHCID 178418339Butyllithium

Product 1

HCID 57475766HCID 57475766, compoundYield 89.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

n-Butyllithium (2.64 M, 37.9 mL) was added dropwise to a solution of 1,3-dibromobenzene (23.5 g) in tetrahydrofuran (469 mL) at −78° C. The mixture was stirred at the same temperature for 30 minutes, and then tetrahydro-4H-pyran-4-one (10.0 g) was added dropwise. The mixture was stirred at the same temperature for 30 minutes and then warmed to room temperature. After stirring at room temperature for four hours, an ammonium chloride solution was added to the reaction mixture to terminate the reaction. The aqueous layer was extracted with ethyl acetate, and the organic layer was washed with water and brine. The organic layer was dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the resulting residue was dissolved in toluene (400 mL). p-Toluenesulfonic acid monohydrate (2 g) was added and the mixture was stirred with heating under reflux for two hours. The reaction mixture was cooled to room temperature and purified by NH-silica gel column chromatography to obtain the title compound (21.4 g).

Workup

  1. stirringThe mixture was stirred at the same temperature for 30 minutes
  2. stirringAfter stirring at room temperature for four hours
  3. customto terminate
  4. customthe reaction
  5. extractionThe aqueous layer was extracted with ethyl acetate
  6. washthe organic layer was washed with water and brine
  7. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  8. customThe solvent was evaporated under reduced pressure
  9. dissolutionthe resulting residue was dissolved in toluene (400 mL)
  10. additionp-Toluenesulfonic acid monohydrate (2 g) was added
  11. stirringthe mixture was stirred
  12. temperaturewith heating
  13. temperatureunder reflux for two hours
  14. temperatureThe reaction mixture was cooled to room temperature
  15. custompurified by NH-silica gel column chromatography

Sources & evidence

ORD record
ord-2a6a71fe65634746ace5200ca018e5a2
Source dataset
uspto-grants-2015_02
Patent number
US08946210B2

Reaction notes

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