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

HRID 1040576Notes

Reaction equation

HRID 1040576 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-3f1208076f2c4d9997bdf6a7a909c64e
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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