Azobisisobutyronitrile → HCID 54529045, compound

HRID 862581Notes

Reaction equation

HRID 862581 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([C:17]([N+:20]([O-:22])=[O:21])=[CH:18][CH:19]=1)[CH2:5][CH:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8].BrN1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N.[C:43]1(=[O:53])[NH:47][C:46](=[O:48])[C:45]2=[CH:49][CH:50]=[CH:51][CH:52]=[C:44]12.[K].C(=O)(O)[O-].[Na+]>C(Cl)(Cl)(Cl)Cl.N(C(C)(C)C#N)=NC(C)(C)C#N>[C:43]1(=[O:53])[N:47]([CH2:1][C:2]2[CH:3]=[C:4]([C:17]([N+:20]([O-:22])=[O:21])=[CH:18][CH:19]=2)[CH2:5][CH:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])[C:46](=[O:48])[C:45]2=[CH:49][CH:50]=[CH:51][CH:52]=[C:44]12

Participants

8

Reactant 5

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 516892Sodium BicarbonateHCID 24194345Phthalimide potassium saltHCID 54156513HCID 54156513, compound

Product 1

HCID 54529045HCID 54529045, compoundYield 56.3%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

A mixture of diethyl 3-methyl-6-nitrobenzylmalonate (25.0 g, 80.8 mmol), N-bromosuccinimide (18.5 g, 103.9 mmol), and azobisisobutyronitrile (AlBN, 1.1 g) in carbon tetrachloride (400 mL) was refluxed for 11 h, while 3×100 mg of AlBN were added every 3 h during the reaction. The insoluble material formed was removed by filtration and the filtrate was concentrated. The residue was dissolved in DMF (100 mL) and potassium phthalimide (13.5 g, 72.9 mmol) was added. The mixture was stirred for 3 h at 5°~60° C., poured into saturated sodium bicarbonate, and extracted with a 1:1 mixture of toluene and ethyl acetate. The organic layers were washed with brine, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography with 4:1 hexane/ethyl acetate to give 18.66 g of the title compound (51%).

Workup

  1. additionwere added every 3 h during the reaction
  2. customThe insoluble material formed
  3. customwas removed by filtration
  4. concentrationthe filtrate was concentrated
  5. dissolutionThe residue was dissolved in DMF (100 mL)
  6. extractionextracted with a 1:1 mixture of toluene and ethyl acetate
  7. washThe organic layers were washed with brine
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated
  10. customThe residue was purified by silica gel column chromatography with 4:1 hexane/ethyl acetate

Sources & evidence

ORD record
ord-d9c6abd3fb784c6696a2508ad879057e
Source dataset
uspto-grants-1998_02
Patent number
US05719152

Reaction notes

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