Methanol → Dimethyl 4-bromoisophthalate

HRID 33736

Reaction equation

HRID 33736 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=O)=[CH:4][C:3]=1[C:11]([OH:13])=[O:12].S(=O)(=O)(O)O.[CH3:19]CCCCC.[CH3:25][OH:26]>>[CH3:25][O:26][C:6](=[O:8])[C:5]1[CH:9]=[CH:10][C:2]([Br:1])=[C:3]([C:11]([O:13][CH3:19])=[O:12])[CH:4]=1

Participants

5

Reactant 4

HCID 887Methanol2×HCID 1118Sulfuric AcidHCID 8058HexaneHCID 813614-Bromo-1,3-benzenedicarboxylic acid

Product 1

HCID 2824912Dimethyl 4-bromoisophthalateYield 90%

Procedure

To a solution of 4-bromoisophthalic acid 201 (10 g, 40.8 mmol) in methanol (150 mL) was added concentrated sulfuric acid (3.5 mL). The solution mixture was heated at reflux temperature for 24 hours. After the reaction was complete, the methanol solvent was removed under reduced pressure. The residue was made basic with saturated sodium bicarbonate (NaHCO3). The solution was extracted with ethyl acetate. The extract was washed with water and dried over sodium sulfate (Na2SO4). Removal of solvent gave oil, which solidified at ambient temperature. The solid was titurated twice with 20 mL of methanol and hexane (1:3) to give 8 g (90%) of 4-bromoisophthalic acid dimethyl ester 202: 1H NMR (400 MHz, CDCl3) δ 3.93 (s, 3H), 3.93 (s, 3H), 7.74 (d, J=8 Hz, 1H), 7.95 (dd, J=2 Hz, J=8 Hz, 1H), 8.43 (d, J=2 Hz, 1H).

Workup

  1. temperatureThe solution mixture was heated
  2. temperatureat reflux temperature for 24 hours
  3. customthe methanol solvent was removed under reduced pressure
  4. extractionThe solution was extracted with ethyl acetate
  5. washThe extract was washed with water
  6. dry with materialdried over sodium sulfate (Na2SO4)
  7. customRemoval of solvent
  8. customgave oil, which
  9. customsolidified at ambient temperature

Sources & evidence

ORD record
ord-fb58d91d786943b4be3dabb93d882007
Source dataset
uspto-grants-2008_09
Patent number
US07429651B2

Linked notes

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