N-bromobutanimide → Methyl 2-(bromomethyl)-5-nitrobenzoate

HRID 2379369Notes

Reaction equation

HRID 2379369 reaction equation
[CH3:1][C:2]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[Br:15]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[Br:15][CH2:1][C:2]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 4377758Methyl 2-methyl-5-nitrobenzoate

Product 1

HCID 14552709Methyl 2-(bromomethyl)-5-nitrobenzoateYield 103.8%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

A mixture of methyl 2-methyl-5-nitrobenzoate (2.51 g, 12.9mmol) and benzoyl peroxide (containing approx. 25% water) (164 mg, 0.51 mmol) in carbon tetrachloride (50 ml) was purged with nitrogen before removing 12 ml of the solvent by distillation. N-Bromosuccinimide (2.30 g, 12.9 mmol) was then added in small portions to the refluxing mixture under irradiation (60W) and the mixture heated at reflux for 2.5 h under nitrogen. The succinimide was removed by filtration and the filtrate evaporated in vacuo to give crude methyl 2-bromomethyl-5-nitrobenzoate (3.67 g) as a yellow oil. To this was added sodium sulphite (2.43 g, 19.3 mmol) and water (10 ml) and the mixture heated at 90° C. for 3 h. The resulting solution was allowed to cool to room temperature and the solid formed was collected, washed with cold water (2×5 ml), then diethyl ether (3×10 ml), and dried under high vacuum in the presence of phosphorus pentoxide. Two more crops were similarly collected to afford the title product (1.46 g, 38%) as a white solid. mp 290°-297° C. 1H NMR (360 MHz, D6-DMSO) δ 3.84 (3H, s), 4.34 (2H, s), 7.68 (1H, d, J=8.5 Hz),8.30 (1H, dd, J=8.5 and 2.6 Hz), 8.41 (1H, d, J=2.5 Hz). MS (FAB) 274 (M-1).

Workup

  1. customwas purged with nitrogen
  2. custombefore removing 12 ml of the solvent
  3. distillationby distillation
  4. temperaturethe mixture heated
  5. temperatureat reflux for 2.5 h under nitrogen
  6. customThe succinimide was removed by filtration
  7. customthe filtrate evaporated in vacuo

Sources & evidence

ORD record
ord-05cd45b735fb41b881665ab382754739
Source dataset
uspto-grants-1994_11
Patent number
US05360802

Reaction notes

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