Azobisisobutyronitrile → HCID 66677560, compound

HRID 2404353Notes

Reaction equation

HRID 2404353 reaction equation
[CH3:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[C:10]([F:13])([F:12])[F:11].BrN1C(=O)CCC1=O.CC(N=NC(C#N)(C)C)(C#N)C.Cl.[C:35]([O:39][C:40](=[O:44])[CH2:41][NH:42][CH3:43])([CH3:38])([CH3:37])[CH3:36].C([O-])([O-])=O.[K+].[K+]>C(#N)C.CCOC(C)=O.O>[C:6]([C:5]1[CH:8]=[CH:9][C:2]([CH2:1][N:42]([CH3:43])[CH2:41][C:40]([O:39][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:44])=[C:3]([C:10]([F:11])([F:12])[F:13])[CH:4]=1)#[N:7]

Participants

9

Reactant 5

HCID 6547AzobisisobutyronitrileHCID 11430Potassium CarbonateHCID 67184N-bromobutanimideHCID 27755984-Methyl-3-(trifluoromethyl)benzonitrileHCID 11252350Sarcosine t-butyl ester hydrochloride

Product 1

HCID 66677560HCID 66677560, compoundYield 70%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

A solution of 4-methyl-3-(trifluoromethyl)benzonitrile (1.85 g, 10 mmol), N-bromosuccinimide (2.14 g, 12.0 mmol) and AIBN (0.033 g, 0.2 mmol) in ACN (40 mL) was heated under reflux for 18 hours. The reaction mixture was diluted with EtOAc and water. The suspension was filtered and the filtrate was separated. The organic phase was washed with brine, dried (MgSO4) and concentrated under vacuum. The residue was purified by flash chromatography (silica, iso-hexane/EtOAc). The material was treated with sarcosine tert-butyl ester hydrochloride (0.516 g, 2.84 mmol) and K2CO3 (0.980 g, 7.1 mmol) in ACN (10 mL). The mixture was heated at 70° C. for 18 hours. The solvent was evaporated under vacuum. The residue was dissolved in a mixture of DCM and water and then poured through a hydrophobic frit. The solvent was evaporated under vacuum. The residue was purified by flash chromatography (silica, iso-hexane/EtOAc) to afford the title compound (0.543 g, 70%). 1H NMR (CDCl3, 400 MHz) δ δ 8.15 (1H, d, J=8.2 Hz), 7.90 (1H, s), 7.83 (1H, d, J=8.2 Hz), 3.90 (2H, s), 3.26 (2H, s), 2.37 (3H, s), 1.48 (9H, s).

Workup

  1. temperatureunder reflux for 18 hours
  2. filtrationThe suspension was filtered
  3. customthe filtrate was separated
  4. washThe organic phase was washed with brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated under vacuum
  7. customThe residue was purified by flash chromatography (silica, iso-hexane/EtOAc)
  8. customThe solvent was evaporated under vacuum
  9. dissolutionThe residue was dissolved in a mixture of DCM and water
  10. additionpoured through a hydrophobic frit
  11. customThe solvent was evaporated under vacuum
  12. customThe residue was purified by flash chromatography (silica, iso-hexane/EtOAc)

Sources & evidence

ORD record
ord-8ec9e252f7404aa3a03e164fc431f173
Source dataset
uspto-grants-2014_08
Patent number
US08802704B2

Reaction notes

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