Methanol → Methyl 3-bromobenzoate

HRID 1053599Notes

Reaction equation

HRID 1053599 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6].[CH3:11]O>S(=O)(=O)(O)O>[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([O:7][CH3:11])=[O:6]

Participants

4

Reactant 2

HCID 887MethanolHCID 114563-Bromobenzoic acid

Product 1

HCID 12070Methyl 3-bromobenzoateYield 92.5%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

A solution of 3-bromobenzoic acid (50 g, 248.73 mmol, 1.00 equiv.) in methanol (500 mL) and 98% sulfuric acid (5 mL) was heated at reflux for about 15 hours. After cooling to ambient temperature, the solution was concentrated in vacuo and water (300 mL) was added to the resulting residue. The pH of the solution was adjusted to about 9 by adding sodium carbonate. Standard extractive workup with dichloromethane (3×200 mL) gave a residue that was then dried in an oven to give the title product as an off-white solid (49.5 g; yield=92.5%). 1H NMR (300 MHz, CDCl3) δ: 8.20 (t, J=1.8 Hz, 1H), 7.97-8.01 (m, 1H), 7.69-7.73 (m, 1H), 7.32 (t, J=8.1 Hz, 1H), 3.95 (s, 3H).

Workup

  1. temperatureat reflux for about 15 hours
  2. concentrationthe solution was concentrated in vacuo and water (300 mL)
  3. additionwas added to the resulting residue
  4. additionby adding sodium carbonate
  5. customStandard extractive workup with dichloromethane (3×200 mL) gave a residue that
  6. customwas then dried in an oven

Sources & evidence

ORD record
ord-716e655cb7504e64854fe163258382c5
Source dataset
uspto-grants-2016_07
Patent number
US09394239B2

Reaction notes

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