N-bromobutanimide → Dimethyl 3-(bromomethyl)phthalate

HRID 240669Notes

Reaction equation

HRID 240669 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:5](=[C:10]([CH3:14])[CH:11]=[CH:12][CH:13]=1)[C:6]([O:8][CH3:9])=[O:7].[Br:16]N1C(=O)CCC1=O>C(#N)C>[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:5](=[C:10]([CH2:14][Br:16])[CH:11]=[CH:12][CH:13]=1)[C:6]([O:8][CH3:9])=[O:7]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 12562468Dimethyl 3-methylphthalate

Product 1

HCID 22464988Dimethyl 3-(bromomethyl)phthalateYield 83.6%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
70 °C

Procedure

A stirred mixture of 3-methyl-phthalic dimethyl ester (12.1 g, 57.9 mmol) and N-bromosuccinimide (12.4 g, 69.5 mmol) in acetonitrile (150 mL) was heated at 70° C. (oil bath), while a 200 W light bulb situated 2 cm away was shining on the reaction mixture overnight. The resulting mixture was cooled and concentrated. The residue was dissolved in ethyl acetate (150 mL), washed with water (3×50 mL) and brine (50 mL), and dried (MgSO4). Solvent was removed in vacuo, and the residue was purified by flash chromatography (SiO2, Hexane:EtOAc 8:2) to give 3-bromomethyl-phthalic dimethyl ester (13.9 g, 83%) as a solid: 1H NMR (CDCl3) δ 7.94-7.90 (dd, J=1.1 and 7.9 Hz, 1H), 7.65-7.62 (dd, J=1.0 and 6.9 Hz, 1H), 7.47 (t, J=7.8H, 1H), 4.54 (s, 2H), 3.97 (s, 3H), 3.90 (s, 3H).

Workup

  1. customaway was shining on the reaction mixture overnight
  2. temperatureThe resulting mixture was cooled
  3. concentrationconcentrated
  4. dissolutionThe residue was dissolved in ethyl acetate (150 mL)
  5. washwashed with water (3×50 mL) and brine (50 mL)
  6. dry with materialdried (MgSO4)
  7. customSolvent was removed in vacuo
  8. customthe residue was purified by flash chromatography (SiO2, Hexane:EtOAc 8:2)

Sources & evidence

ORD record
ord-62a5be5a8edc4526aa871ecb08e24a1d
Source dataset
uspto-grants-2014_02
Patent number
US08648096B2

Reaction notes

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