Azobisisobutyronitrile → 6-(2-Chlorophenyl)-5-(4-chlorophenyl)-2-(2,2-dimethylpropanoyl)furo[2,3-b]pyridine-3-carbaldehyde

HRID 8812

Reaction equation

HRID 8812 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[N:13]=[C:12]2[O:14][C:15]([C:18](=[O:23])[C:19]([CH3:22])([CH3:21])[CH3:20])=[C:16]([CH3:17])[C:11]2=[CH:10][C:9]=1[C:24]1[CH:29]=[CH:28][C:27]([Cl:30])=[CH:26][CH:25]=1.BrN1C(=[O:37])CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N.C[N+]1([O-])CCOCC1>C(Cl)(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[N:13]=[C:12]2[O:14][C:15]([C:18](=[O:23])[C:19]([CH3:22])([CH3:21])[CH3:20])=[C:16]([CH:17]=[O:37])[C:11]2=[CH:10][C:9]=1[C:24]1[CH:25]=[CH:26][C:27]([Cl:30])=[CH:28][CH:29]=1

Participants

6

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 82029Methyl morpholine oxideHCID 102525661-[6-(2-Chlorophenyl)-5-(4-chlorophenyl)-3-methylfuro[2,3-b]pyridin-2-yl]-2,2-dimethylpropan-1-one

Product 1

HCID 100953686-(2-Chlorophenyl)-5-(4-chlorophenyl)-2-(2,2-dimethylpropanoyl)furo[2,3-b]pyridine-3-carbaldehyde

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A 10 mL rb flask equipped with a magnetic stir bar was charged with 0.227 g (0.52 mmol) of the product of Example 89, 0.101 g (0.57 mmol) of N-bromosuccinimide, 3 mL CCl4 and ca. 5 mg of 2,2′-azobisisobutyronitrile (AIBN). The reaction mixture was heated to reflux under a nitrogen atmosphere for 2 h then cooled to room temperature and filtered. The filtrate was evaporated in vacuo, and the residue was then redissolved in 2 mL of DMSO. The solution containing the crude bromination product was transferred to a 10 mL reaction tube of a CEM Corporation Discover 300 Watt microwave reactor and 73 mg (0.62 mmol) of N-methylmorpholine-N-oxide was added. The reaction vessel was sealed, placed in the microwave reactor and heated at 150° C. for 2–3 min. After the reaction mixture had cooled to room temperature, it was partitioned between EtOAc and 10% aq. NaHSO4 and extracted. The organic layer was washed with 10% aq. NaHSO4, water, brine, dried (MgSO4), filtered and evaporated. The residue was purified on a silica gel flash chromatography column eluted with 0–10% EtOAc-hexane. Evaporation of the purified fractions and drying in vacuo afforded the title compound. HPLC/MS: 452.1 (M+1), 454.0 (M+3); Rt=4.63 min.

Workup

  1. customA 10 mL rb flask equipped with a magnetic stir bar
  2. temperatureThe reaction mixture was heated
  3. temperatureto reflux under a nitrogen atmosphere for 2 h
  4. filtrationfiltered
  5. customThe filtrate was evaporated in vacuo
  6. dissolutionthe residue was then redissolved in 2 mL of DMSO
  7. additionThe solution containing the crude bromination product
  8. additionwas added
  9. customThe reaction vessel was sealed
  10. temperatureheated at 150° C. for 2–3 min
  11. temperatureAfter the reaction mixture had cooled to room temperature
  12. customit was partitioned between EtOAc and 10% aq. NaHSO4
  13. extractionextracted
  14. washThe organic layer was washed with 10% aq. NaHSO4, water, brine
  15. dry with materialdried (MgSO4)
  16. filtrationfiltered
  17. customevaporated
  18. customThe residue was purified on a silica gel flash chromatography column
  19. washeluted with 0–10% EtOAc-hexane
  20. customEvaporation of the purified fractions
  21. customdrying in vacuo

Sources & evidence

ORD record
ord-5d4a5433cbe84b68be4d18623d3dc161
Source dataset
uspto-grants-2006_08
Patent number
US07091216B2

Linked notes

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