Iodine chloride → 6-Amino-2-fluoro-3-iodo-benzonitrile

HRID 871175Notes

Reaction equation

HRID 871175 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([F:10])[C:3]=1[C:4]#[N:5].C(=O)(O)[O-].[Na+].[I:16]Cl>C(Cl)Cl.CO>[NH2:1][C:2]1[C:3]([C:4]#[N:5])=[C:6]([F:10])[C:7]([I:16])=[CH:8][CH:9]=1

Participants

6

Reactant 3

HCID 24640Iodine chlorideHCID 516892Sodium BicarbonateHCID 5226592-Amino-6-fluorobenzonitrile

Product 1

HCID 265983476-Amino-2-fluoro-3-iodo-benzonitrileYield 43.4%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 2-amino-6-fluorobenzonitrile (3 g, 0.022 mol) in CH2Cl2 (200 mL) and MeOH (50 mL) was added sodium bicarbonate (3.7 g, 0.044 mmol) and ICl (3.75 g, 0.023 mol) in CH2Cl2 (20 mL). The suspension was stirred at room temperature for 2 h. The reaction mixture was concentrated and the residue was partitioned between CH2Cl2 and water. The organic layer was washed with Na2S2O3, water, and brine. The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The crude material was triturated with ether. Filtration gave the title compound as a brown solid (2.5 g, 43% yield). LC/MS: Example 104A @ 2.86 min (RT) (Condition G). MS (ES): m/z=262.93, [M+H]+. 1H NMR (400 MHz, CDCl3) δ ppm 7.60 (1 hr, dd, J=8.78, 7.03 Hz), 6.39 (1 hr, d, J=8 Hz).

Workup

  1. concentrationThe reaction mixture was concentrated
  2. customthe residue was partitioned between CH2Cl2 and water
  3. washThe organic layer was washed with Na2S2O3, water, and brine
  4. dry with materialThe organic layer was dried over Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customThe crude material was triturated with ether
  7. filtrationFiltration

Sources & evidence

ORD record
ord-e00b5454d3d041d6b66a11c965ac8ff2
Source dataset
uspto-grants-2015_03
Patent number
US08969586B2

Reaction notes

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