Furfural → ([4-Bromo-2,6-dimethylphenyl]furan-2-yl)methanol

HRID 1193025

Reaction equation

HRID 1193025 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5](I)=[C:4]([CH3:10])[CH:3]=1.C([Mg]Cl)(C)C.[O:16]1[CH:20]=[CH:19][CH:18]=[C:17]1[CH:21]=[O:22].[Cl-].[NH4+]>O1CCCC1>[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([C:18]2[CH:19]=[CH:20][O:16][C:17]=2[CH2:21][OH:22])=[C:4]([CH3:10])[CH:3]=1

Participants

6

Reactant 4

HCID 7362FurfuralHCID 25517Ammonium ChlorideHCID 27355735-Bromo-2-iodo-1,3-dimethylbenzeneHCID 178418918HCID 178418918, compound

Product 1

HCID 66709611([4-Bromo-2,6-dimethylphenyl]furan-2-yl)methanolYield 82.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

4-Bromo-2,6-dimethyl-1-iodobenzene (5 g, 16 mmol) is dissolved in dry tetrahydrofuran (20 ml) and cooled to −78° C. under an atmosphere of dry nitrogen. Isopropylmagnesium chloride (2M solution in tetrahydrofuran, 10 ml, 20 mmol) is added dropwise with vigorous stirring over 30 minutes. When the addition is complete, the reaction is allowed to warm to room temperature and is stirred for 30 minutes at room temperature. The reaction mixture is cooled to −78° C. and a solution of 2-furaldehyde (2.4 g, 25 mmol) in dry tetrahydrofuran (10 ml) is added dropwise over 30 minutes. Once the addition is complete, the mixture is allowed to warm to room temperature and stirring continued for 2 hours. A solution of saturated aqueous ammonium chloride (30 ml). is added, and the mixture is extracted with dichloromethane (3×25 ml). The organic extracts are combined, washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give ([4-bromo-2,6-dimethylphenyl]furan-2-yl)methanol (3.71 g).

Workup

  1. additionWhen the addition
  2. temperatureto warm to room temperature
  3. stirringis stirred for 30 minutes at room temperature
  4. temperatureThe reaction mixture is cooled to −78° C.
  5. additionOnce the addition
  6. temperatureto warm to room temperature
  7. stirringstirring
  8. waitcontinued for 2 hours
  9. additionis added
  10. extractionthe mixture is extracted with dichloromethane (3×25 ml)
  11. washwashed with brine
  12. dry with materialdried over anhydrous magnesium sulfate
  13. filtrationfiltered
  14. customthe filtrate is evaporated under reduced pressure
  15. customThe residue is purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-0be7fb479df94a41b7e743df13130fc0
Source dataset
uspto-grants-2014_03
Patent number
US08680339B2

Linked notes

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