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

HRID 1040879Notes

Reaction equation

HRID 1040879 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-337fc51db9144817affbcf55b3aa4062
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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