Hydrazine → 1H-1-Benzazepine

HRID 1630701Notes

Reaction equation

HRID 1630701 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-aa1121c262714d76b4d2b75f4be47a86
Source dataset
uspto-grants-2014_07
Patent number
US08791101B2

Reaction notes

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