Iodine → Methyl 3-iodo-4-methylbenzoate

HRID 2071099Notes

Reaction equation

HRID 2071099 reaction equation
[I:1]I.N[C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][C:13]=1[CH3:14])[C:7]([O:9][CH3:10])=[O:8].[O-]S([O-])=O.[Na+].[Na+]>CC#N.O>[I:1][C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][C:13]=1[CH3:14])[C:7]([O:9][CH3:10])=[O:8]

Participants

6

Reactant 3

HCID 807IodineHCID 24437Sodium SulfiteHCID 337778Methyl 3-amino-4-methylbenzoate

Product 1

HCID 13614033Methyl 3-iodo-4-methylbenzoateYield 68.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

To a stirring mixture of 23.0 g (90.6 mmol) of I2 and 5.4 mL (45.5 mmol) of tert-butylnitrile in 40 mL of CH3CN at 35° C. was added 5.0 g (30.3 mmol) of methyl 3-amino-4-methylbenzoate in 4 portions. Stirring was continued with cooling to r.t. in the dark (light off only). After 2.5 h, 400 mL of Na2SO3 in H2O was added gradually. The layers were separated, and the organic layer was washed with 80 mL of brine, dried over Na2SO4, filtered, and concentrated. Purification by flash silica gel chromatography (5% EtOAc/hexanes) provided 5.7 g of methyl 3-iodo-4-methylbenzoate as a red liquid with some impurity in approximately 68% yield.

Workup

  1. customThe layers were separated
  2. washthe organic layer was washed with 80 mL of brine
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by flash silica gel chromatography (5% EtOAc/hexanes)

Sources & evidence

ORD record
ord-c548142babd84dfdb9061179cb3666bb
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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