Iodine → 2,6-Dichloro-5-fluoro-4-iodonicotinonitrile

HRID 75939

Reaction equation

HRID 75939 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.C([N-]C(C)C)(C)C.[Li+].[Cl:21][C:22]1[N:29]=[C:28]([Cl:30])[C:27]([F:31])=[CH:26][C:23]=1[C:24]#[N:25].[I:32]I.[O-]S([O-])(=S)=O.[Na+].[Na+]>C1COCC1>[Cl:21][C:22]1[N:29]=[C:28]([Cl:30])[C:27]([F:31])=[C:26]([I:32])[C:23]=1[C:24]#[N:25]

Participants

8

Conditions

Temperature
-78 °C

Procedure

To a solution of diisopropylamine (15.9 g, 157 mmol) in THF (400 ml) at −78° C. was added n-butyllithium (2.5 M hexanes, 154 mmol), and the solution was stirred at −78° C. for 30 minutes. The lithium diisopropylamide solution was then added slowly dropwise to a −78° C. solution of 2,6-dichloro-5-fluoronicotinonitrile (10.0 g, 52.3 mmol) and iodine (26.5 g, 104 mmol) in THF (175 ml). Upon completion of the addition, the reaction was allowed to warm slowly to room temperature, and stirred at room temperature for 12 hours. An aqueous 10% Na2S2O3 solution (500 ml) was added and the reaction was extracted with EtOAc (3×300 ml). The combined organic fractions were dried over Na2SO4, filtered, and then concentrated to give the title compound (14.5 g, 87%) as a brown solid that was used without further purification.

Workup

  1. additionUpon completion of the addition
  2. temperatureto warm slowly to room temperature
  3. stirringstirred at room temperature for 12 hours
  4. extractionthe reaction was extracted with EtOAc (3×300 ml)
  5. dry with materialThe combined organic fractions were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-808231e5a3284e5489291033d5ce8883
Source dataset
uspto-grants-2014_09
Patent number
US08835465B2

Linked notes

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