Hydrazine hydrate (1:1) → 5,5-Dimethyl-2,3,4,5-tetrahydro-1H-benzo[b]azepin-7-amine

HRID 1040880Notes

Reaction equation

HRID 1040880 reaction equation
O.NN.[CH3:4][C:5]1([CH3:19])[CH2:11][CH2:10][CH2:9][NH:8][C:7]2[CH:12]=[CH:13][C:14]([N+:16]([O-])=O)=[CH:15][C:6]1=2>[Pd].C(O)C>[CH3:4][C:5]1([CH3:19])[CH2:11][CH2:10][CH2:9][NH:8][C:7]2[CH:12]=[CH:13][C:14]([NH2:16])=[CH:15][C:6]1=2

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 578538055,5-Dimethyl-7-nitro-2,3,4,5-tetrahydro-1H-benzo[b]azepine

Product 1

HCID 672643035,5-Dimethyl-2,3,4,5-tetrahydro-1H-benzo[b]azepin-7-amineYield 91%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

Added 6 mL of ethanol, 10% Palladium on activated carbon (50% wet with water for safety) (60 mg), and hydrazine monohydrate (89 ul) to 5,5-Dimethyl-7-nitro-2,3,4,5-tetrahydro-1H-benzo[b]azepine (101 mg, 0.459 mmol). Heated reaction to 60° C. for 22 hours. Filtered reaction through Celite, and concentrated under reduced pressure. Purified with normal phase silica gel chromatography eluting with 5% methylene chloride in methanol to obtain a brown oil, 5,5-Dimethyl-2,3,4,5-tetrahydro-1H-benzo[b]azepin-7-ylamine (79 mg, 91%). LCMS: m/z=190.99 (M+H+), 1H NMR (400 MHz, CDCl3) δ 6.73 (d, 1H, J=2.0 Hz), 6.55 (d, 1H, J=8.1 Hz), 6.43 (dd, 1H, J=8.1, 1.5 Hz), 3.40 (br s, 3H), 2.97 (m, 2H), 1.86 (m, 2H), 1.59 (m, 2H), 1.38 (s, 6H).

Workup

  1. temperatureHeated
  2. customreaction to 60° C. for 22 hours
  3. filtrationFiltered
  4. customreaction through Celite
  5. concentrationconcentrated under reduced pressure
  6. customPurified with normal phase silica gel chromatography
  7. washeluting with 5% methylene chloride in methanol

Sources & evidence

ORD record
ord-9d5e031598fc41a794d88c48846c0346
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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