Selenium Dioxide → 2-(2,6-Dichloro-phenylamino)-1,6-dimethyl-9-oxo-8,9-dihydro-1H-imidazo[4,5-h]isoquinoline-7-carbaldehyde

HRID 1863897Notes

Reaction equation

HRID 1863897 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[NH:9][C:10]1[N:11]([CH3:26])[C:12]2[C:21]3[C:20](=[O:22])[NH:19][C:18]([CH3:23])=[C:17]([CH3:24])[C:16]=3[CH:15]=[CH:14][C:13]=2[N:25]=1.[Se](=O)=[O:28]>O1CCOCC1>[Cl:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([Cl:1])[C:3]=1[NH:9][C:10]1[N:11]([CH3:26])[C:12]2[C:21]3[C:20](=[O:22])[NH:19][C:18]([CH:23]=[O:28])=[C:17]([CH3:24])[C:16]=3[CH:15]=[CH:14][C:13]=2[N:25]=1

Participants

4

Reactant 2

HCID 24007Selenium DioxideHCID 99082472-(2,6-Dichloro-phenylamino)-1,6,7-trimethyl-1,8-dihydro-imidazo[4,5-h]isoquinolin-9-one

Product 1

HCID 108622852-(2,6-Dichloro-phenylamino)-1,6-dimethyl-9-oxo-8,9-dihydro-1H-imidazo[4,5-h]isoquinoline-7-carbaldehydeYield 72.4%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a 200 mL round bottom flask equipped with a stir bar was added 2-(2,6-dichloro-phenylamino)-1,6,7-trimethyl-1,8-dihydro-imidazo[4,5-h]isoquinolin-9-one (2.4 g, 6.2 mmol), selenium dioxide (2.0 g, 18 mmol) and dioxane (150 mL). The flask was fitted with a condenser and heated to reflux for 4.5 h. The reaction was then removed from heat and allowed to cool to room temperature. The slightly opaque solution was filtered through celite and washed with dichloromethane:methanol (9:1). The solution was concentrated and the resulting residue triturated with dichloromethane to produce 2-(2,6-dichloro-phenylamino)-1,6-dimethyl-9-oxo-8,9-dihydro-1H-imidazo[4,5-h]isoquinoline-7-carbaldehyde (1.8 g, 72%) as a brownish yellow solid, which was used without further purification. 1H NMR (400 MHz, DMSO-d6+TFA) δ 10.65 (s, 1H), 10.24 (s, 1H), 7.96 (d, 1H, J=8.6 Hz), 7.78 (d, 1H, J=8.6 Hz), 7.70 (d, 2H, J=7.8 Hz), 7.49 (d, 2H, J=7.8 Hz), 4.15 (s, 3H), 2.70 (s, 3H); ESMS (m/z): found, 401.

Workup

  1. customTo a 200 mL round bottom flask equipped with a stir bar
  2. customThe flask was fitted with a condenser
  3. temperatureheated
  4. temperatureto reflux for 4.5 h
  5. customThe reaction was then removed
  6. temperaturefrom heat
  7. filtrationThe slightly opaque solution was filtered through celite
  8. washwashed with dichloromethane:methanol (9:1)
  9. concentrationThe solution was concentrated
  10. customthe resulting residue triturated with dichloromethane

Sources & evidence

ORD record
ord-a37d07101f8b4c00a2cfa7e52684158d
Source dataset
uspto-grants-2009_12
Patent number
US07625880B2

Reaction notes

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