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

HRID 2387976Notes

Reaction equation

HRID 2387976 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+].[CH2:17]([Sn](CCCC)(CCCC)C=C)[CH2:18]CC.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>[CH:17]([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)=[CH2:18]

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 81998TributylvinyltinHCID 522689Potassium Fluoride2×HCID 584766238-iodo-2,3,4,5-tetrahydro-1H-1-benzazepine-2,5-dione

Product 1

HCID 673365978-vinyl-3,4-dihydro-1H-1-benzazepine-2,5-dioneYield 40%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
100 °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), tributylethenylstannane (0.58 mL, 2.0 mmol), and Pd(PPh3)4 (116 mg, 0.1 mmol). The reaction mixture was allowed to stir at 100° 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 mixture was allowed to stir for an additional 40 min. The mixture was filtered over Celite® and the organic solution was separated, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was treated with n-pentane and filtered. The resulting solid was purified by column chromatography to provide 8-vinyl-3,4-dihydro-1H-1-benzazepine-2,5-dione (80 mg, 40%).

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. additionThe residue was treated with n-pentane
  10. filtrationfiltered
  11. customThe resulting solid was purified by column chromatography

Sources & evidence

ORD record
ord-9330e24832ce4a0482c1bcb12d3b7433
Source dataset
uspto-grants-2012_09
Patent number
US08268992B2

Reaction notes

Loading…