Allyl bromide → 1-Allyl-9-nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one

HRID 1040951Notes

Reaction equation

HRID 1040951 reaction equation
[N+:1]([C:4]1[C:9]2[NH:10][CH2:11][CH2:12][NH:13][C:14](=[O:15])[C:8]=2[CH:7]=[CH:6][CH:5]=1)([O-:3])=[O:2].[H-].[Na+].[CH2:18](Br)[CH:19]=[CH2:20]>CN(C=O)C>[CH2:20]([N:10]1[C:9]2[C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=[CH:7][C:8]=2[C:14](=[O:15])[NH:13][CH2:12][CH2:11]1)[CH:19]=[CH2:18]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 27716119-Nitro-1,2,3,4-tetrahydro-5H-1,4-benzodiazepin-5-one

Product 1

HCID 672645191-Allyl-9-nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-oneYield 71.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

9-Nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one (763 mg, 3.67 mmol) was dissolved in anh DMF (10 ml). NaH (60% dispersion in mineral oil) (147 mg, 3.67 mmol) was added followed by allyl bromide (310 μL, 3.67 mmol). The resulting mixture was stirred at rt for 2 h. Reaction mixture was concentrated, diluted with CH2Cl2, and washed with H2O. The organic layer was dried over MgSO4, filtered, concentrated, and purified with silica gel chromatography (0-100% EtOAc in hexanes) to afford 1-Allyl-9-nitro-1,2,3,4-tetrahydro-benzo[e][1,4]diazepin-5-one as an orange solid (647 mg, 71%). mp 80-82° C.; LCMS: m/z=248.27 (M+H+); 1H NMR (400 MHz, CDCl3) δ 8.67 (m, 1H), 8.30 (dd, J=8.3 Hz, 1.5 Hz, 1H), 8.17 (dd, J=7.6 Hz, 1.5 Hz, 1H), 6.78 (t, J=7.8 Hz, 1HO, 5.85 (m, 1H), 5.29 (m, 2H), 4.22 (m, 2H), 3.74 (m, 2H), 3.58 (m, 2H).

Workup

  1. customReaction mixture
  2. concentrationwas concentrated
  3. additiondiluted with CH2Cl2
  4. washwashed with H2O
  5. dry with materialThe organic layer was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified with silica gel chromatography (0-100% EtOAc in hexanes)

Sources & evidence

ORD record
ord-f290ce3ca90f49499a07c69226461d0e
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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