Methanol → 5,5-Dimethyl-7-nitro-2,3,4,5-tetrahydro-1H-benzo[b]azepine

HRID 1687187Notes

Reaction equation

HRID 1687187 reaction equation
[CH3:1][C:2]1([CH3:17])[CH2:8][CH2:7][C:6](=O)[NH:5][C:4]2[CH:10]=[CH:11][C:12]([N+:14]([O-:16])=[O:15])=[CH:13][C:3]1=2.CO>C1COCC1>[CH3:1][C:2]1([CH3:17])[CH2:8][CH2:7][CH2:6][NH:5][C:4]2[CH:10]=[CH:11][C:12]([N+:14]([O-:16])=[O:15])=[CH:13][C:3]1=2

Participants

4

Reactant 2

HCID 887MethanolHCID 578538385,5-Dimethyl-7-nitro-1,3,4,5-tetrahydro-benzo[b]azepin-2-one

Product 1

HCID 578538055,5-Dimethyl-7-nitro-2,3,4,5-tetrahydro-1H-benzo[b]azepineYield 72%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Combined 5,5-Dimethyl-7-nitro-1,3,4,5-tetrahydrobenzo[b]azepin-2-one (89 mg, 0.38 mmol), Borane-THF complex, 1M in THF (1.9 mL, 1.9 mmol) and 3 mL anhydrous THF. Heated reaction to reflux for 1 hour. Let reaction cool to room temperature, added methanol and concentrated under reduced pressure. Dissolved residue in methylene chloride and washed with saturated sodium bicarbonate solution. Purified with normal phase chromatography eluting with 10% ethyl acetate in hexane to yield a yellow solid, 5,5-Dimethyl-7-nitro-2,3,4,5-tetrahydro-1H-benzo[b]azepine (60 mg, 72%). mp 99° C.; LCMS: m/z=221.06 (M+H+), 1H NMR (400 MHz, CDCl3) δ 8.26 (d, 1H, J=2.3 Hz), 7.91 (dd, 1H, J=8.6, 2.5 Hz), 6.68 (d, 1H, J=8.8 Hz), 4.28 (br s, 1H), 3.16 (m, 2H), 1.91 (m, 2H), 1.72 (m, 2H), 1.41 (s, 6H).

Workup

  1. temperatureHeated
  2. customreaction
  3. temperatureto reflux for 1 hour
  4. customreaction
  5. concentrationconcentrated under reduced pressure
  6. washDissolved residue in methylene chloride and washed with saturated sodium bicarbonate solution
  7. customPurified with normal phase chromatography
  8. washeluting with 10% ethyl acetate in hexane

Sources & evidence

ORD record
ord-9981f3d7c7794baf92b366087a8953ce
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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