Sodium Azide → Methyl 5-azidomethyl-2-nitrobenzoate

HRID 862568Notes

Reaction equation

HRID 862568 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([N+:12]([O-:14])=[O:13])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].BrN1C(=O)CCC1=O.[N-:23]=[N+:24]=[N-:25].[Na+]>C(Cl)(Cl)(Cl)Cl.[Cl-].[Na+].O.N(C(C)(C)C#N)=NC(C)(C)C#N>[N:23]([CH2:1][C:2]1[CH:3]=[CH:4][C:5]([N+:12]([O-:14])=[O:13])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8])=[N+:24]=[N-:25]

Participants

7

Reactant 3

HCID 33557Sodium AzideHCID 67184N-bromobutanimideHCID 3314122Methyl 5-methyl-2-nitrobenzoate

Product 1

HCID 19698364Methyl 5-azidomethyl-2-nitrobenzoateYield 56%

Reagents, catalysts & solvents 3

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of methyl 5-methyl-2-nitrobenzoate (5.5 g, 30 mmol), N-bromosuccinimide (NBS, 5.87 g, 33 mmol), and azobisisobutyronitrile (AlBN, 200 mg) in carbon tetrachloride (60 mL) was refluxed for 3 h. The insoluble material formed was removed by filtration and the filtrate was concentrated. The residue was dissolved in DMF (10 mL) and sodium azide (2.92 g, 45 mmol) was added. The mixture was stirred for 2 h at 50° C., poured into brine, and extracted with a 1:1 mixture of toluene and ethyl acetate. The organic layers were washed with brine, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography with 4:1 hexane/ethyl acetate to give 3.97 g of the title compound (56%).

Workup

  1. temperaturewas refluxed for 3 h
  2. customThe insoluble material formed
  3. customwas removed by filtration
  4. concentrationthe filtrate was concentrated
  5. dissolutionThe residue was dissolved in DMF (10 mL)
  6. extractionextracted with a 1:1 mixture of toluene and ethyl acetate
  7. washThe organic layers were washed with brine
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated
  10. customThe residue was purified by silica gel column chromatography with 4:1 hexane/ethyl acetate

Sources & evidence

ORD record
ord-7c698477cf64466a9842f66780c05685
Source dataset
uspto-grants-1998_02
Patent number
US05719152

Reaction notes

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