Ethyl Acetate → 8-methyl-3,4-dihydro-1H-1-benzazepine-2,5-dione

HRID 2387975Notes

Reaction equation

HRID 2387975 reaction equation
I[C:2]1[CH:14]=[CH:13][C:5]2[C:6](=[O:12])[CH2:7][CH2:8][C:9](=[O:11])[NH:10][C:4]=2[CH:3]=1.[F-].[K+].[Sn](C)(C)(C)[CH3:18].CCOC(C)=O>CN(C=O)C.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:18][C:2]1[CH:14]=[CH:13][C:5]2[C:6](=[O:12])[CH2:7][CH2:8][C:9](=[O:11])[NH:10][C:4]=2[CH:3]=1

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 11661TetramethyltinHCID 522689Potassium Fluoride2×HCID 584766238-iodo-2,3,4,5-tetrahydro-1H-1-benzazepine-2,5-dione

Product 1

HCID 584766398-methyl-3,4-dihydro-1H-1-benzazepine-2,5-dioneYield 32%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

To a degassed solution of 8-iodo-3,4-dihydro-1H-1-benzazepine-2,5-dione (0.3 g, 1.0 mmol) in DMF (5 mL) was added CuI (19 mg, 0.1 mmol), KF (116 mg, 2.0 mmol), Me4Sn (0.28 mL, 2.0 mmol), and Pd(PPh3)4 (116 mg, 0.1 mmol). The reaction mixture was allowed to stir at 120° C. for 4 h. After being allowed to cool to rt, EtOAc (50 mL) and a 1M aqueous KF solution (25 mL) were added and the solution was allowed to stir for an additional 40 min. The mixture was filtered over Celite®. The organic solution was separated, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography to provide 8-methyl-3,4-dihydro-1H-1-benzazepine-2,5-dione (60 mg, 32%).

Workup

  1. temperatureto cool to rt
  2. stirringto stir for an additional 40 min
  3. filtrationThe mixture was filtered over Celite®
  4. customThe organic solution was separated
  5. washwashed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-a6d0320eb7634e69abab38e9d6cc2a90
Source dataset
uspto-grants-2012_09
Patent number
US08268992B2

Reaction notes

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