Iodine → 2-Amino-4-difluoromethyl-5-iodo-benzoic acid methyl ester

HRID 1894099Notes

Reaction equation

HRID 1894099 reaction equation
[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7]([CH:10]([F:12])[F:11])=[CH:6][C:5]=1[NH2:13].[I:15]I>CCO.[O-]S([O-])(=O)=O.[Ag+].[Ag+]>[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[C:8]([I:15])[C:7]([CH:10]([F:12])[F:11])=[CH:6][C:5]=1[NH2:13]

Participants

5

Reactant 2

HCID 807IodineHCID 591644252-Amino-4-difluoromethyl-benzoic acid methyl ester

Product 1

HCID 591644452-Amino-4-difluoromethyl-5-iodo-benzoic acid methyl esterYield 90.1%

Reagents, catalysts & solvents 2

HCID 159865Silver sulfateCatalystHCID 702EthanolSolvent

Procedure

To a solution of 2-amino-4-difluoromethyl-benzoic acid methyl ester (1.98 g, 9.84 mmol) in EtOH (75 mL) were added Ag2SO4 (3.08 g, 1 equiv) and I2 (2.50 g, 1 equiv) and the resulting mixture was stirred at r.t. for 1 hour. The mixture was filtered through a pad of celite and washed with EtOH. The solution was concentrated in vacuo and then diluted with AcOEt. The organic phase was washed with sat. aq NaHCO3, 1M aq Na2S2O3 and brine and dried (Na2SO4). The solution was concentrated in vacuo to afford the title compound as an off-white solid (2.9 g, 90% yield). ES-MS: m/z 369.2 [M+CH3CN+H]+, rt 5.87 min.

Workup

  1. filtrationThe mixture was filtered through a pad of celite
  2. washwashed with EtOH
  3. concentrationThe solution was concentrated in vacuo
  4. additiondiluted with AcOEt
  5. washThe organic phase was washed with sat. aq NaHCO3, 1M aq Na2S2O3 and brine
  6. dry with materialdried (Na2SO4)
  7. concentrationThe solution was concentrated in vacuo

Sources & evidence

ORD record
ord-7f4664b3109d4d1bbd64e04913abf39c
Source dataset
uspto-grants-2013_08
Patent number
US08513268B2

Reaction notes

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