Sodium Iodide → HCID 58182714, compound

HRID 2199615

Reaction equation

HRID 2199615 reaction equation
[NH2:1][C:2]1[C:9](Br)=[CH:8][C:5](C#N)=[CH:4][N:3]=1.[I-:11].[Na+].CN[C@@H]1CCCC[C@H]1[NH:21][CH3:22]>O1CCOCC1.[Cu]I>[I:11][C:9]1[C:2]([NH2:1])=[N:3][CH:4]=[C:5]([N+:21]#[C-:22])[CH:8]=1

Participants

6

Reactant 3

HCID 5238Sodium IodideHCID 14912506-Amino-5-bromopyridine-3-carbonitrileHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamine

Product 1

HCID 58182714HCID 58182714, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

The mixture of 6-amino-5-bromonicotinonitrile (3.315 g, 15.9 mmol, 1 eq), sodium iodide (4.77 g, 2 eq), copper(I) iodide (303 mg, 0.1 eq), and trans-N,N′-dimethylcyclohexane-1,2-diamine (0.52 mL, 0.2 eq) in anhydrous dioxane (40 mL under nitrogen atmosphere was stirred at 120° C. for 20 hours. The mixture was cooled to room temperature then partitioned between ethyl acetate and aqueous ammonium chloride. The organic layer was isolated, further washed with saturated aqueous sodium bicarbonate, brine, and dried with anhydrous sodium sulfate. The upper solution was decanted, concentrated, and the crude solid residue was subject to a column chromatography started first with EtOAc-Hex (1:5 to 1:1) followed by MeOH—CHCl3 (1:100 to 1:20). Product containing fractions were all collected and concentrated. The solid residue was triturated with EtOAc-Hex (1:4) yielding 3-iodo-5-isocyanopyridin-2-amine as an off-white solid in the amount of 2.75 g upon filtration.

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. customthen partitioned between ethyl acetate and aqueous ammonium chloride
  3. customThe organic layer was isolated
  4. washfurther washed with saturated aqueous sodium bicarbonate, brine
  5. dry with materialdried with anhydrous sodium sulfate
  6. customThe upper solution was decanted
  7. concentrationconcentrated
  8. additionProduct containing fractions
  9. customall collected
  10. concentrationconcentrated
  11. customThe solid residue was triturated with EtOAc-Hex (1:4)

Sources & evidence

ORD record
ord-7e1ee5ac571f4c2ca06910a31bacfc15
Source dataset
uspto-grants-2016_06
Patent number
US09359336B2

Linked notes

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