Iodine → HCID 21471464, compound

HRID 2295217Notes

Reaction equation

HRID 2295217 reaction equation
[C:1]([C:3]1[C:4]([CH:20]([CH3:22])[CH3:21])=[N:5][C:6]2[C:11]([C:12]=1[C:13]1[CH:18]=[CH:17][C:16]([F:19])=[CH:15][CH:14]=1)=[CH:10][CH:9]=[CH:8][CH:7]=2)#[CH:2].CC(N=NC(C#N)(C)C)(C#N)C.[I:35]I>C([SnH](CCCC)CCCC)CCC.CCOCC>[F:19][C:16]1[CH:15]=[CH:14][C:13]([C:12]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[N:5]=[C:4]([CH:20]([CH3:22])[CH3:21])[C:3]=2/[CH:1]=[CH:2]/[I:35])=[CH:18][CH:17]=1

Participants

6

Reactant 3

HCID 807IodineHCID 6547Azobisisobutyronitrile2×HCID 21471459HCID 21471459, compound

Product 1

HCID 21471464HCID 21471464, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 5948TributylstannaneSolvent2×

Conditions

Temperature
120 °C

Procedure

A mixture of 3-Ethynyl-4-(4-fluorophenyl)-2-(1-methylethyl)quinoline (1.500 gm, 5.18 mmol) (the preparation of which is described in Example 8) and AIBN (15 mg) in tri-n-butylstannyl hydride (2.1 ml) was rapidly heated to 120° C. After 3 minutes of heating, the mixture was treated with additional Bu3SnH (0.6 ml) and the temperature of the reaction was raised to 130° C. Approximately 15 mg of AIBN was added to the reaction mixture of 0.5, 1, and 2 hours after heating was initiated. After 2.5 hours, the mixture was cooled to room temperature, diluted with Et2O (30 ml) and treated with solid I2 (3.86 gm, 15.2 mmol). The dark reaction mixture was stirred for 1 hour, then quenched with 10% Na2SO3 in saturated NaHCO3. The layers were shaken and separated. The ethereal layer was washed with brine, dried (Na2 SO4), filtered and stripped to yield a liquid/solid residue. The residue was chromatographed (flash, Merck SiO2, 4% EtOAc in hexane) to give slightly impure (E)-4-(4-Fluorophenyl)-3-(2-iodoethenyl)-2-(1-methylethyl)-quinoline as a solid. Recrystallization of the solid from hot hexane gave (E)-4-(4-Fluorophenyl)-3-(2-iodoethenyl)-2-(1-methylethyl)quinoline (1.725 gm, 80%) as light yellow crystals.

Workup

  1. customthe preparation of which
  2. temperatureAfter 3 minutes of heating
  3. temperaturethe temperature of the reaction was raised to 130° C
  4. temperatureafter heating
  5. temperaturethe mixture was cooled to room temperature
  6. customThe dark reaction mixture
  7. customquenched with 10% Na2SO3 in saturated NaHCO3
  8. stirringThe layers were shaken
  9. customseparated
  10. washThe ethereal layer was washed with brine
  11. customdried (Na2 SO4)
  12. filtrationfiltered
  13. customto yield a liquid/solid residue
  14. customThe residue was chromatographed (flash, Merck SiO2, 4% EtOAc in hexane)

Sources & evidence

ORD record
ord-f43c56213e4a46f4abbf27a5d5f9e4b6
Source dataset
uspto-grants-1997_11
Patent number
US05691322

Reaction notes

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