Carbon Tetrachloride → Methyl 2-(bromomethyl)-3-nitrobenzoate

HRID 483052Notes

Reaction equation

HRID 483052 reaction equation
[CH3:1][C:2]1[C:11]([N+:12]([O-:14])=[O:13])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[Br:15]N1C(=O)CCC1=O.C(Cl)(Cl)(Cl)Cl>CCOCC.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[Br:15][CH2:1][C:2]1[C:11]([N+:12]([O-:14])=[O:13])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

6

Reactant 3

HCID 5943Carbon TetrachlorideHCID 67184N-bromobutanimideHCID 601165Methyl 2-methyl-3-nitrobenzoate

Product 1

HCID 1487795Methyl 2-(bromomethyl)-3-nitrobenzoateYield 52.6%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalyst2×HCID 3283Diethyl EtherSolvent

Procedure

A mixture of 100.0 g of methyl 2-methyl-3-nitrobenzoate, 100.0 g of N-bromosuccinimide, 3.0 g of dibenzoyl peroxide and 1000 ml of carbon tetrachloride was refluxed for 24 hours. The reaction mixture was cooled, 3.0 g of dibenzoyl peroxide added, and refluxing continued an additional 24 hours. The reaction mixture was cooled, filtered and the filtrate concentrated in vacuo. The crude reaction product was dissolved in ether and the organic solution washed sequentially with saturated sodium sulfite (500 ml), water (2×500 ml), 2.5% sodium hydroxide (500 ml), water (2×500 ml) and saturated brine (500 ml). The organic solution was dried over magnesium sulfate, filtered and the solvent evaporated in vacuo giving a pale yellow oily solid. Recrystallization from 350 ml of 1-chlorbutane/cyclohexane (2:1) gave 73.9 g of methyl 2-bromomethyl-3-nitrobenzoate, m.p. 67°-70°.

Workup

  1. temperaturewas refluxed for 24 hours
  2. temperatureThe reaction mixture was cooled
  3. temperaturerefluxing
  4. temperatureThe reaction mixture was cooled
  5. filtrationfiltered
  6. concentrationthe filtrate concentrated in vacuo
  7. customThe crude reaction product
  8. washthe organic solution washed sequentially with saturated sodium sulfite (500 ml), water (2×500 ml), 2.5% sodium hydroxide (500 ml), water (2×500 ml) and saturated brine (500 ml)
  9. dry with materialThe organic solution was dried over magnesium sulfate
  10. filtrationfiltered
  11. customthe solvent evaporated in vacuo
  12. customgiving a pale yellow oily solid
  13. customRecrystallization from 350 ml of 1-chlorbutane/cyclohexane (2:1)

Sources & evidence

ORD record
ord-436f6d04cd3e4d13b01ce114d168277b
Source dataset
uspto-grants-1986_03
Patent number
US04578108

Reaction notes

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