反応 #329904

ord-5f33ccf406034e1dbb379159b510b051

反応条件

温度
-78°CELSIUS
詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    その他The mixture was sonicated at room temperature under argon for 2 min
  2. 2
    その他resulting in a deep red solution
  3. 3
    温度to warm to room temperature
  4. 4
    workup.STIRRINGthe reaction was stirred at room temperature for 4.3 h
  5. 5
    その他The reaction was partitioned between EtOAc and water
  6. 6
    洗浄the combined organics were washed with brine
  7. 7
    乾燥dried over MgSO4
  8. 8
    濃縮concentrated under reduced pressure
  9. 9
    その他Purification by flash chromatography (6 to 50% EtOAc-hexanes gradient)

実験手順

To a −78° C. solution of triphenyl((2,6,6-trimethylcyclohex-1-enyl)methyl)phosphonium bromide (24) (0.3787 g, 0.79 mmol) and 18-crown-6 (0.0246 g, 0.093 mmol) in CH2Cl2 (7 mL) was added potassium tert-butoxide (0.0991 g, 0.88 mmol). The mixture was sonicated at room temperature under argon for 2 min, resulting in a deep red solution. The mixture was cooled to −78° C. then a solution of 3-iodo-4-methylbenzaldehyde (0.1742 g, 0.71 mmol) in CH2Cl2 (3 mL+2 mL) was added and stirred for 5 min. The reaction mixture was allowed to warm to room temperature. Additional phosphonium salt 24 (0.3725 g, 1.6 mmol), 3-iodo-4-methylbenzaldehyde (0.2538 g, 1.7 mmol) and potassium tert-butoxide (0.1548 g, 1.38 mmol) were then added and the reaction was stirred at room temperature for 4.3 h. The reaction was partitioned between EtOAc and water then the combined organics were washed with brine, dried over MgSO4 and concentrated under reduced pressure. Purification by flash chromatography (6 to 50% EtOAc-hexanes gradient) gave (E)-2-iodo-1-methyl-4-(2-(2,6,6-trimethylcyclohex-1-enyl)vinyl)benzene as a white solid. Yield (0.26 g, 45%): 1H NMR (400 MHz, DMSO-d6) δ 7.91 (d, J=1.6 Hz, 1H), 7.44 (dd, J=7.6, 1.2 Hz, 1H), 7.29 (d, J=7.2 Hz, 1H), 6.71 (d, J=16.4 Hz, 1H), 6.28 (6, J=16.8 Hz, 1H), 2.35 (s, 3H), 2.01 (t, J=6.4 Hz, 2H), 1.72 (s, 3H), 1.57-1.64 (m, 2H), 1.43-1.47 (m, 2H), 1.04 (s, 6H).

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US08653142B2uspto-grants-2014_02