Hydrazine hydrate (1:1) → 7-Amino-1-(2-methoxyethyl)-1,3,4,5-tetrahydrobenzo[b]azepin-2-one

HRID 1687154Notes

Reaction equation

HRID 1687154 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][N:5]1[C:11](=[O:12])[CH2:10][CH2:9][CH2:8][C:7]2[CH:13]=[C:14]([N+:17]([O-])=O)[CH:15]=[CH:16][C:6]1=2.O.NN>CCO.[Pd]>[NH2:17][C:14]1[CH:15]=[CH:16][C:6]2[N:5]([CH2:4][CH2:3][O:2][CH3:1])[C:11](=[O:12])[CH2:10][CH2:9][CH2:8][C:7]=2[CH:13]=1

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 672641631-(2-Methoxy-ethyl)-7-nitro-1,3,4,5-tetrahydro-benzo[b]azepin-2-one

Product 1

HCID 434466107-Amino-1-(2-methoxyethyl)-1,3,4,5-tetrahydrobenzo[b]azepin-2-oneYield 54%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

To a solution of the above 1-(2-methoxy-ethyl)-7-nitro-1,3,4,5-tetrahydro-benzo[b]azepin-2-one in EtOH (10 mL) was sequentially added 10% Pd/C (120 mg) and hydrazine-monohydrate (1 mL). The solution was warmed to reflux for 2.5 h, cooled, filtered through celite, and repeatedly evaporated from toluene to remove residual hydrazine. The residue was recrystallized from EtOAc/heptane to afford transparent prisms of 7-amino-1-(2-methoxy-ethyl)-1,3,4,5-tetrahydro-benzo[b]azepin-2-one (345 mg, 54%) that had the following properties: mp: 134-135° C.; LC/MS (ESI+): 235 (M+H); 1H-NMR (CDCl3, 400 MHz): δ 7.08 (d, J=8.4, 1H), 6.60 (d, J=8.4, 1H), 6.51 (s, 1H), 4.20 (br s, 1H), 3.65 (m, 2H), 3.53 (m, 2H), 3.28 (s, 3H), 2.60 (br s, 1H), 2.27 (m, 2H), 1.58 (m, 3H).

Workup

  1. temperatureThe solution was warmed
  2. temperatureto reflux for 2.5 h
  3. temperaturecooled
  4. filtrationfiltered through celite
  5. customrepeatedly evaporated from toluene
  6. customto remove residual hydrazine
  7. customThe residue was recrystallized from EtOAc/heptane

Sources & evidence

ORD record
ord-a4717aa9482b49cd8d1145bba629fc3e
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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