Cyclohexanone → 4-[(4-Bromophenyl)(cyclohexylidene)methyl]-3-methylphenol

HRID 229150Notes

Reaction equation

HRID 229150 reaction equation
[C:1]1(=O)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[Br:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]([C:17]2[CH:22]=[CH:21][C:20]([OH:23])=[CH:19][C:18]=2[CH3:24])=O)=[CH:11][CH:10]=1.C([O-])([O-])=O.[K+].[K+]>C1COCC1.[Zn].Cl[Ti](Cl)(Cl)Cl>[Br:8][C:9]1[CH:14]=[CH:13][C:12]([C:15](=[C:1]2[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]2)[C:17]2[CH:22]=[CH:21][C:20]([OH:23])=[CH:19][C:18]=2[CH3:24])=[CH:11][CH:10]=1

Participants

7

Reactant 3

HCID 7967CyclohexanoneHCID 11430Potassium CarbonateHCID 68654122(4-Bromophenyl)(4-hydroxy-2-methylphenyl)methanone

Product 1

HCID 686545414-[(4-Bromophenyl)(cyclohexylidene)methyl]-3-methylphenolYield 81.5%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 24193Titanium TetrachlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a slurry of zinc powder (1.15 g, 17.59 mmol) in THF (10 mL) was added TiCl4 (0.90 mL, 8.21 mmol) dropwise. The mixture was heated at reflux for 1 h. A mixture of cyclohexanone (0.64 mL, 6.17 mmol) and (4-bromophenyl)(4-hydroxy-2-methylphenyl)methanone (28) (0.60 g, 2.06 mmol) in THF (10 mL) was added dropwise and continued to stir at reflux for 20 min. Upon cooling, the reaction mixture was poured into a 10% aqueous K2CO3 solution. The quenched reaction mixture was filtered through a pad of Celite and the pad was washed with EtOAc. The filtrate was dried over MgSO4, filtered, and concentrated to yield 0.60 g (81%) of the compound 29. 1H NMR (400 MHz, CDCl3): δ 1.50-1.63 (m, 6H), 1.96-2.01 (m, 2H), 2.05 (s, 3H), 2.27-2.28 (m, 2H), 4.54 (s, 1H), 6.60-6.62 (m, 2H), 6.93-6.95 (m, 1H), 6.98 (d, J=8.4 Hz, 2H), 7.35 (d, J=8.4 Hz, 2H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 1 h
  3. additionwas added dropwise
  4. temperatureat reflux for 20 min
  5. temperatureUpon cooling
  6. customThe quenched reaction mixture
  7. filtrationwas filtered through a pad of Celite
  8. washthe pad was washed with EtOAc
  9. dry with materialThe filtrate was dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-648459bddd0f40a089be83d3d13abf34
Source dataset
uspto-grants-2009_07
Patent number
US07560589B2

Reaction notes

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