Dimethylformamide → tert-Butyl 7-cyano-1,2,4,5-tetrahydro-3H-benzo[d]azepine-3-carboxylate

HRID 395265Notes

Reaction equation

HRID 395265 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:14][CH2:13][C:12]2[CH:15]=[CH:16][C:17](OS(C(F)(F)F)(=O)=O)=[CH:18][C:11]=2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:27][N:28](C)C=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N>[C:1]([O:5][C:6]([N:8]1[CH2:14][CH2:13][C:12]2[CH:15]=[CH:16][C:17]([C:27]#[N:28])=[CH:18][C:11]=2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 181732813-(tert-butoxycarbonyl)-7-trifluoromethylsulfonyloxy-2,3,4,5-tetrahydro-1H-3-benzazepine

Product 1

HCID 18173275tert-Butyl 7-cyano-1,2,4,5-tetrahydro-3H-benzo[d]azepine-3-carboxylateYield 23%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 3-(tert-butoxycarbonyl)-7-trifluoromethylsulfonyloxy-2,3,4,5-tetrahydro-1H-3-benzazepine (4.78 g, 12.1 mmol), zinc cyanide (1.42 g, 15.6 mmol) and tetrakis-triphenylphosphine palladium (0) (1.4 g, 1.2 mmol, 10 mol %), in dry dimethylformamide (50 ml) was stirred at 100° C. for 3 h under argon. After cooling to room temperature the reaction mixture was diluted with ethyl acetate (120 ml) and filtered. The filtrate was washed with saturated aqueous sodium bicarbonate (100 ml), then water (2×50 ml), then brine (50 ml). The organic layer was dried over sodium sulfate and evaporated in vacuo to give brown oil, which was purified by chromatography on silica gel with 20-100% ethyl acetate-hexane elution to give the title compound (0.765 g, 23%) as a brown oil.

Workup

  1. filtrationfiltered
  2. washThe filtrate was washed with saturated aqueous sodium bicarbonate (100 ml)
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. customevaporated in vacuo
  5. customto give brown oil, which
  6. customwas purified by chromatography on silica gel with 20-100% ethyl acetate-hexane elution

Sources & evidence

ORD record
ord-e77b0838f3bf400e846198660bf0f7a1
Source dataset
uspto-grants-2003_08
Patent number
US06605607B1

Reaction notes

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