Ammonia → 6-Iodo-4-methylquinolin-2(1H)-one

HRID 2112810Notes

Reaction equation

HRID 2112810 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[NH:8][C:7](=[O:12])[CH:6]=[C:5]2[CH3:13].[Na+].[I-:15].CNCCNC.N>O1CCOCC1.[Cu]I.O>[I:15][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[NH:8][C:7](=[O:12])[CH:6]=[C:5]2[CH3:13]

Participants

8

Reactant 4

HCID 222AmmoniaHCID 5238Sodium Iodide2×HCID 8070N,N'-Dimethylethylenediamine2×HCID 63244626-Bromo-4-methylquinolin-2-ol

Product 1

HCID 126863636-Iodo-4-methylquinolin-2(1H)-one

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst2×HCID 962WaterSolventHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
110 °C

Procedure

A mixture of 5.0 g (21.0 mmol) of 6-bromo-4-methyl-1H-quinolin-2-one and 400 mg (2.1 mmol) of CuI in 21 mL 1,4-dioxane is evacuated and gassed with argon. Then 6.3 g (42.0 mmol) of NaI and 0.45 mL (4.2 mmol) of N,N′-dimethylethylenediamine are added, the mixture is evacuated again and gassed with argon before being heated overnight to 110° C. HPLC analysis of the mixture shows approximately 20% reaction. Therefore another 400 mg (2.1 mmol) of CuI, 6.3 g (42.0 mmol) of NaI, 0.45 mL (4.2 mmol) of N,N′-dimethylethylenediamine, and 21 mL of 1,4-dioxane are added and this mixture is heated overnight again to 110° C. To complete the reaction, the above procedure is repeated another three times. After cooling, the suspension is combined with 10% NH3 solution and water and the precipitated product is filtered off. This is then washed with 10% NH3 solution, water, isopropanol, DIPE, EtOAc, and DCM and dried overnight in the air. The product, which still contains approximately 20% educt, is further reacted without purification. Yield: 3.0 g (40% of theoretical); C10H8INO (M=285.081); calc.: molpeak (M+H)+: 286; found: molpeak (M+H)+: 286; HPLC-MS: 5.0 min (method B).

Workup

  1. customis evacuated
  2. customthe mixture is evacuated again
  3. temperaturebefore being heated overnight to 110° C
  4. customapproximately 20% reaction
  5. customthe reaction
  6. temperatureAfter cooling
  7. filtrationthe precipitated product is filtered off
  8. washThis is then washed with 10% NH3 solution, water, isopropanol, DIPE, EtOAc, and DCM
  9. customdried overnight in the air
  10. customThe product, which still contains approximately 20% educt, is further reacted without purification
  11. custom5.0 min (method B)

Sources & evidence

ORD record
ord-b06a514e2647456394e3020842c33fb2
Source dataset
uspto-grants-2009_04
Patent number
US07524862B2

Reaction notes

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