N-bromobutanimide → 1-(Bromomethyl)-4-methoxy-2-nitrobenzene

HRID 1914675

Reaction equation

HRID 1914675 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[Br:13]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl>[Br:13][CH2:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 871374-Methyl-3-nitroanisole

Product 1

HCID 37478301-(Bromomethyl)-4-methoxy-2-nitrobenzeneYield 59.1%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
85 °C

Procedure

To a solution of 4-methyl-3-nitroanisole (16.53 mL; 119.64 mmol; 1 eq), in CCl4 (500 mL) is added N-bromosuccinimide (21.29 g; 119.64 mmol; 1 eq) and azoisobutyronitrile (392.9 mg; 2.39 mmol; 0.02 eq). The mixture is heated at 85° C. for 20 h. The solution is cooled down to room temperature and the precipitate of succinimide is removed by filtration. The filtrate is concentrated to afford a yellow oil. The oil crystallizes after one night at −25° C. It is redissolved in EtOAc (15 mL) and petroleum ether is added. After 2 h at −25° C., the compound recrystallizes. After filtration and washing with petroleum ether, the solid is dried under vacuum to afford 17.4 g (59%) of the title compound as a liquid. 1H NMR (DMSO-d6) δ 7.68 (d, J=8 Hz, 1H), 7.56 (d, J=3 Hz, 1H), 7.33 (dd, J=8.0, 3.0 Hz, 1H), 4.89 (s, 2H), 3.87 (s, 3H). HPLC (max plot) 99%; Rt 4.09 min.

Workup

  1. temperatureThe solution is cooled down to room temperature
  2. customthe precipitate of succinimide is removed by filtration
  3. concentrationThe filtrate is concentrated
  4. customto afford a yellow oil
  5. customThe oil crystallizes after one night at −25° C
  6. dissolutionIt is redissolved in EtOAc (15 mL)
  7. additionpetroleum ether is added
  8. customthe compound recrystallizes
  9. filtrationAfter filtration
  10. washwashing with petroleum ether
  11. customthe solid is dried under vacuum

Sources & evidence

ORD record
ord-f239c2fc4bd14fdf83b92f423f9a9511
Source dataset
uspto-grants-2013_12
Patent number
US08614215B2

Linked notes

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