7-nitro-2,3,4,5-tetrahydro-1H-1-benzazepin-2-one → 7-Nitro-2,3,4,5-tetrahydro-1H-benzo[B]azepine

HRID 1686944Notes

Reaction equation

HRID 1686944 reaction equation
[N+:1]([C:4]1[CH:15]=[CH:14][C:7]2[NH:8][C:9](=O)[CH2:10][CH2:11][CH2:12][C:6]=2[CH:5]=1)([O-:3])=[O:2].B.C1COCC1>C1COCC1>[N+:1]([C:4]1[CH:15]=[CH:14][C:7]2[NH:8][CH2:9][CH2:10][CH2:11][CH2:12][C:6]=2[CH:5]=1)([O-:3])=[O:2]

Participants

4

Reactant 2

HCID 3561757-nitro-2,3,4,5-tetrahydro-1H-1-benzazepin-2-oneHCID 2723981Borane;tetrahydrofuran

Product 1

HCID 158877537-Nitro-2,3,4,5-tetrahydro-1H-benzo[B]azepineYield 69.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

A solution of 7-Nitro-1,3,4,5-tetrahydro-benzo[b]azepin-2-one (0.34 g, 1.65 mmol) in THF (10 mL) was treated with borane-THF (5 mL, 4.95 mmol) and heated to 60° C. and stirred for 2 h. The mixture was poured in saturated aqueous sodium bicarbonate/ice. The mixture was extracted 2×EtOAc, the organic layers washed with brine and dried (MgSO4), filtered and concentrated on SiO2. Purification by ISCO chromatography (40 gram column, SiO2, gradient 0% to 100% EtOAc in hexane) gave 7-Nitro-2,3,4,5-tetrahydro-1H-benzo[b]azepine (220 mg, 63%). MP: 73-75° C.; 1H-NMR (CDCl3) δ 7.97 (s, 1H), 7.89 (dd, J=2.6, 8.7 Hz, 1H), 6.61 (d, J=8.7 Hz, 1H), 4.42 (br s, 1H), 2.88-2.84 (m, 2H), 1.89-1.78 (m, 4H); LC/MS (ESI+): 193.02 (M+H).

Workup

  1. extractionThe mixture was extracted 2×EtOAc
  2. washthe organic layers washed with brine
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated on SiO2
  6. customPurification by ISCO chromatography (40 gram column, SiO2, gradient 0% to 100% EtOAc in hexane)

Sources & evidence

ORD record
ord-caf2276c4e37464e8b0357cdd141d5b6
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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