Methyl iodide → 1-Methyl-7-nitro-1,3,4,5-tetrahydrobenzo[b]azepin-2-one

HRID 1686884Notes

Reaction equation

HRID 1686884 reaction equation
[N+:1]([C:4]1[CH:15]=[CH:14][C:7]2[NH:8][C:9](=[O:13])[CH2:10][CH2:11][CH2:12][C:6]=2[CH:5]=1)([O-:3])=[O:2].[H-].[Na+].[CH3:18]I>CN(C=O)C>[CH3:18][N:8]1[C:9](=[O:13])[CH2:10][CH2:11][CH2:12][C:6]2[CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[CH:15]=[CH:14][C:7]1=2

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 3561757-nitro-2,3,4,5-tetrahydro-1H-1-benzazepin-2-one

Product 1

HCID 578538961-Methyl-7-nitro-1,3,4,5-tetrahydrobenzo[b]azepin-2-oneYield 87%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

7-Nitro-1,3,4,5-tetrahydro-benzo[b]azepin-2-one (200 mg, 0.97 mmol) was dissolved in anhydrous DMF (3 ml), and treated with sodium hydride (60% in mineral oil, 58 mg, 1.45 mmol) followed by methyl iodide (0.5 ml). The mixture was stirred 18 hours at room temperature, and then partitioned between ethyl acetate (30 ml) and water (30 ml). Washing once with water (30 ml), drying over anhydrous magnesium sulfate and concentration gave a yellow residue. Purification by preparative TLC (40% EtOAc/hexane) gave 1-Methyl-7-nitro-1,3,4,5-tetrahydrobenzo[b]azepin-2-one as a white solid, 185 mg. (87% yield) 1H NMR (400 MHz, DMSO-d6) δ 8.14-8.24 (m, 2H), 7.52-7.60 (m, 1H), 3.40 (s, 3H), 2.75-2.82 (m, 2H), 2.06-2.25 (m, 4H); MS (m/e) 221 (M+1).

Workup

  1. custompartitioned between ethyl acetate (30 ml) and water (30 ml)
  2. washWashing once with water (30 ml)
  3. dry with materialdrying over anhydrous magnesium sulfate and concentration
  4. customgave a yellow residue
  5. customPurification by preparative TLC (40% EtOAc/hexane)

Sources & evidence

ORD record
ord-dee7c5976e5940a684d6e6c56136126a
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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