Hydrazine hydrate (1:1) → HCID 67263881, compound

HRID 1040650Notes

Reaction equation

HRID 1040650 reaction equation
[CH3:1][O:2][C:3]1[C:13]2[CH2:12][CH2:11][CH2:10][C:9](=[O:14])[N:8]([CH3:15])[C:7]=2[CH:6]=[CH:5][C:4]=1[N+:16]([O-])=O.O.NN>[Pd].C(O)C>[NH2:16][C:4]1[CH:5]=[CH:6][C:7]2[N:8]([CH3:15])[C:9](=[O:14])[CH2:10][CH2:11][CH2:12][C:13]=2[C:3]=1[O:2][CH3:1]

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 67264210HCID 67264210, compound

Product 1

HCID 67263881HCID 67263881, compoundYield 93%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Conditions

Temperature
60 °C

Procedure

6-Methoxy-1-methyl-7-nitro-1,3,4,5-tetrahydro-benzo[b]azepin-2-one (530 mg, 2.12 mmol) in a 4:1 mixture of ethanol (17 mL) and hydrazine hydrate (4.5 mL) was heated to 60° C. and to it was added a ¼ mass equivalent of 10% Palladium/Carbon (50% H2O) (135 mg). The reaction was monitored by LC/MS to ensure that complete reduction occurred, and upon completion was cooled to room temperature. The Pd/C was filtered through celite, and the resulting filtrate concentrated to a minimal volume. This was then brought up in ˜120 mL of CH2Cl2 and washed with ˜25 mL of brine to remove excess hydrazine. The organic layer was then dried with MgSO4 and concentrated to give 7-Amino-6-methoxy-1-methyl-1,3,4,5-tetrahydro-benzo[b]azepin-2-one as a yellow gummy solid (432 mg, 93%). 1H-NMR (CDCl3) δ 6.78 (d, J=8.6 Hz, 1H), 6.65 (d, J=8.6 Hz, 1H), 3.81 (br s, 2H), 3.75 (s, 3H), 3.28 (s, 3H), 2.35-2.75 (br pk, 2H), 2.30 (t, J=6.9 Hz, 2H), 2.15 (m, 2H); LC/MS (ESI-pos) m/z 221.13 (M+H).

Workup

  1. temperatureupon completion was cooled to room temperature
  2. filtrationThe Pd/C was filtered through celite
  3. concentrationthe resulting filtrate concentrated to a minimal volume
  4. washwashed with ˜25 mL of brine
  5. customto remove excess hydrazine
  6. dry with materialThe organic layer was then dried with MgSO4
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-7485bd103c394a9e9324e73513a59e6f
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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