Methanol → Methyl 3-iodo-4-methylbenzoate

HRID 1890246Notes

Reaction equation

HRID 1890246 reaction equation
[I:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[CH3:11])[C:5]([OH:7])=[O:6].S(=O)(=O)(O)O.[CH3:17]O>>[CH3:17][O:6][C:5](=[O:7])[C:4]1[CH:8]=[CH:9][C:10]([CH3:11])=[C:2]([I:1])[CH:3]=1

Participants

4

Reactant 3

HCID 887MethanolHCID 1118Sulfuric AcidHCID 6216403-Iodo-4-methylbenzoic acid

Product 1

HCID 13614033Methyl 3-iodo-4-methylbenzoate

Conditions

Temperature
70 °C

Procedure

To a solution of 3-iodo-4-methyl-benzoic acid (10.0 g, 38.2 mmol) in methanol (70 ml) is added concentrated sulfuric acid (0.5 ml). The reaction mixture is heated at 70° C. for 48 hours, cooled to room ambient temperature and then concentrated. After that, ethyl acetate (100 ml) and aqueous NaHCO3 (saturated, 100 ml) solution are added to the residue. The organic layer is separated and washed again with aqueous NaHCO3 (saturated, 100 ml) solution. The organic layer is separated, dried over anhydrous Na2SO4 and concentrated to yield 3-iodo-4-methyl-benzoic acid methyl ester 1. It is used without further purification in the next step. 1H NMR (400 MHz, DMSO-d6) δ 8.31 (s, 1H), 7.87 (d, 1H, J=8.4 Hz), 7.48 (d, 1H, J=8.4 Hz), 3.85 (s, 3H), 3.35 (s, 3H); LC-MS m/z: 277.0 (M+1).

Workup

  1. temperaturecooled to room ambient temperature
  2. concentrationconcentrated
  3. additionAfter that, ethyl acetate (100 ml) and aqueous NaHCO3 (saturated, 100 ml) solution are added to the residue
  4. customThe organic layer is separated
  5. washwashed again with aqueous NaHCO3 (saturated, 100 ml) solution
  6. customThe organic layer is separated
  7. dry with materialdried over anhydrous Na2SO4
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-89fcbe390d1446bc893f6c496f827bae
Source dataset
uspto-grants-2013_08
Patent number
US08507471B2

Reaction notes

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