Acetonitrile → n,n-Dimethyl-2-(7-nitro-1,2,4,5-tetrahydro-3h-3-benzazepin-3-yl)acetamide

HRID 1041378Notes

Reaction equation

HRID 1041378 reaction equation
[N+]([O-])(O)=O.[N+:5]([C:8]1[CH:18]=[CH:17][C:11]2[CH2:12][CH2:13][NH:14][CH2:15][CH2:16][C:10]=2[CH:9]=1)([O-:7])=[O:6].C(#N)C.Cl[CH2:23][C:24]([N:26]([CH3:28])[CH3:27])=[O:25].C(=O)([O-])[O-].[Cs+].[Cs+].[I-].[Cs+]>C(Cl)Cl>[CH3:27][N:26]([CH3:28])[C:24](=[O:25])[CH2:23][N:14]1[CH2:15][CH2:16][C:10]2[CH:9]=[C:8]([N+:5]([O-:7])=[O:6])[CH:18]=[CH:17][C:11]=2[CH2:12][CH2:13]1

Participants

7

Reactant 5

HCID 6342AcetonitrileHCID 10796Cesium carbonateHCID 24601Cesium iodideHCID 758862-chloro-N,N-dimethylacetamideHCID 855770687-Nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine nitrate

Product 1

HCID 57416161n,n-Dimethyl-2-(7-nitro-1,2,4,5-tetrahydro-3h-3-benzazepin-3-yl)acetamideYield 94%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

7-Nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine; compound with nitric acid (763 mg, 2.99 mmol) was suspended in acetonitrile (50.0 mL, 957 mmol) and 2-chloro-N,N-dimethyl-acetamide (400 mg, 3.29 mmol) was added. Cesium carbonate (2.44 g, 7.48 mmol) and cesium iodide (77.7 mg, 0.299 mmol) were added and the reaction was heated at reflux for 3 hours. The reaction was cooled to room temperature and then diluted with DCM (50 mL) and washed with water (50 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. Purification by silica gel chromatography using a gradient of 0-15% MeOH/DCM as the eluting solvent to obtain N,N-Dimethyl-2-(7-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-acetamide as an orange solid (778 mg, 94%). m.p.=94-96° C.; LCMS (m/e) 278 (M+H); 1H-NMR (CDCl3, 400 MHz) δ 8.02-7.97 (m, 2H), 7.25 (d, 1H, J=7.9 Hz), 3.34 (s, 2H), 3.12 (s, 3H), 3.08-3.02 (m, 4H), 2.99 (s, 3H), 2.80-2.73 (m, 4H).

Workup

  1. temperaturethe reaction was heated
  2. temperatureat reflux for 3 hours
  3. washwashed with water (50 mL)
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customPurification by silica gel chromatography

Sources & evidence

ORD record
ord-15b94a77f2db46c9b0aa4e0bf9ffff20
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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