Iodine → HCID 21471283, compound

HRID 2293847Notes

Reaction equation

HRID 2293847 reaction equation
[C:1]([C:3]1[C:4]([CH:22]([CH3:24])[CH3:23])=[N:5][C:6]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:7][C:8]=1[C:9]1[CH:14]=[CH:13][C:12]([F:15])=[CH:11][CH:10]=1)#[CH:2].CC(N=NC(C#N)(C)C)(C#N)C.[I:37]I.CCOC(C)=O>C([SnH](CCCC)CCCC)CCC.CCOCC.CCCCCC>[F:15][C:12]1[CH:13]=[CH:14][C:9]([C:8]2[CH:7]=[C:6]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[N:5]=[C:4]([CH:22]([CH3:24])[CH3:23])[C:3]=2/[CH:1]=[CH:2]/[I:37])=[CH:10][CH:11]=1

Participants

8

Reactant 4

HCID 807IodineHCID 6547Azobisisobutyronitrile2×HCID 8857Ethyl Acetate2×HCID 15099588HCID 15099588, compound

Product 1

HCID 21471283HCID 21471283, compound

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 5948TributylstannaneSolvent2×HCID 8058HexaneSolvent2×

Conditions

Temperature
120 °C

Procedure

A mixture of 3-Ethynyl-4-(4-fluorophenyl)-2-(1-methylethyl)-6-phenylpyridine (1.500 gm, 4.76 mmol) (The preparation of which is described in example 4) and 14 mg of AIBN in tri-n-butylstannyl hydride (BU3SnH) (1.90 ml) was rapidly heated to 120° C. After 4 minutes of heating, the mixture was treated with additional Bu3SnH (0.4 ml) and the temperature of the reaction was raised to 130° C. Approximately 14 mg of AIBN was added to the reaction mixture 0.5, 1.5 and 2.5 hours after heating was initiated. After 4 hours, the mixture was cooled to room temperature, diluted with Et2O (40 ml) and treated with solid I2 (1.92 gm, 7.56 mmol). The dark reaction mixture was stirred for 1.5 hours, then quenched with 10% Na2SO3 in saturated NaHCO3. The layers were shaken and separated. The ethereal layer was washed with brine, dried (Na2SO4), filtered and stripped to yield a yellow oil. Flash chromatography (Merck SiO2, 1% EtOAc in hexane followed by 1.5% EtOAc in hexane afforded (E)-4-(4-Fluorophenyl)-3-(2-iodoethenyl)-2-(1-methylethyl)-6-phenylpyridine as a solid. Recrystallization of the solid from hot hexane gave 1.438 gm (E)-4-(4-Fluorophenyl)-3-(2-iodoethenyl)-2-(1-methylethyl)-6-phenylpyridine. An additional 0.19 gm of compound was obtained from the mother liquor to give a total of 1.628 gm (77%) product. m.p. 111.0°-112.3° C.

Workup

  1. customThe preparation of which
  2. temperatureAfter 4 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. dry with materialdried (Na2SO4)
  12. filtrationfiltered
  13. customto yield a yellow oil

Sources & evidence

ORD record
ord-032bb29b4cff464cbc7bc76afcb87e22
Source dataset
uspto-grants-1997_11
Patent number
US05686433

Reaction notes

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