Methanol → Methyl 3-iodo-4-methylbenzoate

HRID 1924795Notes

Reaction equation

HRID 1924795 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, 1 H), 7.87 (d, 1 H, J=8.4 Hz), 7.48 (d, 1 H, J=8.4 Hz), 3.85 (s, 3 H), 3.35 (s, 3 H); 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-e00af63495984c34b25eeb90ed1ae607
Source dataset
uspto-grants-2012_05
Patent number
US08178563B2

Reaction notes

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