Azobisisobutyronitrile → HCID 57680931, compound

HRID 1163121Notes

Reaction equation

HRID 1163121 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[CH3:12])[N:8]=[C:7]([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[CH:6]=[CH:5]2.CC(N=NC(C#N)(C)C)(C#N)C.C1C(=O)N(Br)C(=[O:34])C1.C([O-])(O)=O.[Na+]>O.C(Cl)(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[CH:12]=[O:34])[N:8]=[C:7]([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[CH:6]=[CH:5]2

Participants

7

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 516892Sodium BicarbonateHCID 57680938HCID 57680938, compound

Product 1

HCID 57680931HCID 57680931, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
90 °C

Procedure

The CCl4 (45 ml) solution of 6-chloro-7-methyl-2-phenylquinoline (753.3 mg, 2.969 mmol), AIBN (48.8 mg, 0.1 eq.) and NBS (898.4 mg, 1.7 eq.) was heated at 80° C. under N2 for 8 h. After that time, the reaction mixture was concentrated in vacuo and the residue was dissolved in EtOAc (60 ml), washed successively with H2O (30 mL), saturated NaS2O3 (30 mL), H2O (30 mL), and brine (30 mL). The organic extract was then dried (MgSO4), filtered and concentrated in vacuo. The residue was dissolved in DMSO (105 mL), and then NaHCO3 (2495 mg, 10 eq.) was added. The reaction mixture was stirred at 90° C. for 3 h. Water (140 mL) was added and the mixture was extracted with EtOAc (3×200 mL). The combined organic extracts were washed with H2O (4×60 mL) and brine (60 mL), and dried (MgSO4), filtered, and concentrated in vacuo. The residue was recrystallized from CHCl3/hexane (20:80, 10 mL) to give 6-chloro-2-phenylquinoline-7-carbaldehyde as pale-yellow solid; 1H NMR (CDCl3, 400 MHz) δ 7.51-7.58 (m, 3H), 7.93 (s, 1H), 8.03 (d, 1H, J=8.8 Hz), 8.18-8.20 (m, 3H), 8.75 (s, 1H), 10.63 (s, 1H); MS (ES+): 268.1/270.0 (M/M+2).

Workup

  1. concentrationAfter that time, the reaction mixture was concentrated in vacuo
  2. dissolutionthe residue was dissolved in EtOAc (60 ml)
  3. washwashed successively with H2O (30 mL), saturated NaS2O3 (30 mL), H2O (30 mL), and brine (30 mL)
  4. extractionThe organic extract
  5. dry with materialwas then dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. dissolutionThe residue was dissolved in DMSO (105 mL)
  9. extractionthe mixture was extracted with EtOAc (3×200 mL)
  10. washThe combined organic extracts were washed with H2O (4×60 mL) and brine (60 mL)
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo
  14. customThe residue was recrystallized from CHCl3/hexane (20:80, 10 mL)

Sources & evidence

ORD record
ord-40cecd33fec346a3ad6b69269f7b8f49
Source dataset
uspto-grants-2010_10
Patent number
US07820662B2

Reaction notes

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