Hydrazine → 1H-1-Benzazepine

HRID 1478674Notes

Reaction equation

HRID 1478674 reaction equation
ClC1([C:8]2[CH:18]=[CH:17][C:11]3[CH:12]=[CH:13][CH:14]=[CH:15][NH:16][C:10]=3[CH:9]=2)C=CC=NN1.NN>C(O)C.[Pd]>[NH:16]1[C:10]2[CH:9]=[CH:8][CH:18]=[CH:17][C:11]=2[CH:12]=[CH:13][CH:14]=[CH:15]1

Participants

5

Reactant 2

HCID 9321HydrazineHCID 669644748-(3-Chloropyridazin-3-yl)benzazepine

Product 1

HCID 155596581H-1-BenzazepineYield 69.8%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

To a solution of the 8-(3-chloropyridazin-3-yl)benzazepine (0.77 g, 2.0 mmol) from step L above in ethanol (50 mL) were added hydrazine (1.0 mL, 20 mmol) and palladium on carbon (0.11 g). The reaction solution was heated under reflux for 16 h, and then it was cooled to room temperature, filtered through a plug of Celite and concentrated under reduced pressure. The crude product was purified by flash column chromatography (dichloromethane to 90:9:1 dichloromethane/methanol/concentrated ammonium hydroxide) to give the racemic benzazepine (0.20 g, 28%) as a yellow foam: 1H NMR (CDCl3, 500 MHz) δ 9.15 (dd, J=4.5, 1.5 Hz, 1H), 8.00 (d, J=2.0 Hz, 1H), 7.84 (dd, J=8.5, 1.5 Hz, 1H), 7.80 (d, J=8.0 Hz, 1H), 7.53 (dd, J=8.5, 5.0 Hz, 1H), 6.92-6.80 (br, 1H), 6.77-6.70 (br, 3H), 4.38 (d, J=8.5 Hz, 1H), 3.98 (d, J=13.0 Hz, 1H), 3.85 (d, J=14.0 Hz, 1H), 3.14-3.08 (m, 1H), 3.01-2.96 (m, 1H), 2.38 (s, 3H), 2.87-2.14 (m, 2H).

Workup

  1. temperatureThe reaction solution was heated
  2. temperatureunder reflux for 16 h
  3. filtrationfiltered through a plug of Celite
  4. concentrationconcentrated under reduced pressure
  5. customThe crude product was purified by flash column chromatography (dichloromethane to 90:9:1 dichloromethane/methanol/concentrated ammonium hydroxide)

Sources & evidence

ORD record
ord-000a4f92dd1e4ebbb724479ec151a455
Source dataset
uspto-grants-2016_08
Patent number
US09403776B2

Reaction notes

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