Iodine → Benzoic acid, 4-amino-2-chloro-5-iodo-, methyl ester

HRID 1911214Notes

Reaction equation

HRID 1911214 reaction equation
[NH2:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([Cl:12])[CH:3]=1.C([O-])([O-])=O.[Ca+2].[I:18]I>CO.C(Cl)Cl>[NH2:1][C:2]1[C:11]([I:18])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([Cl:12])[CH:3]=1.[NH2:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([Cl:12])[C:3]=1[I:18]

Participants

7

Reactant 3

HCID 807IodineHCID 10112Calcium CarbonateHCID 11839197Methyl 4-Amino-2-chlorobenzoate

Product 2

HCID 11839203Benzoic acid, 4-amino-2-chloro-5-iodo-, methyl esterHCID 59625863Methyl 4-amino-2-chloro-3-iodobenzoate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a suspension of compound 70m (1.18 g, 6.38 mmol) and CaCO3 (12.8 mmol, 1.28 g) in MeOH (13 mL) was added a solution of iodine monchloride (6.70 mmol, 1.09 g) in CH2Cl2 (6 mL) dropwise at room temperature. The resulting reaction mixture was stirred at room temperature for 1.5 h. The reaction mixture was concentrated and then partitioned between EtOAc and water. The organic layer was concentrated and purified by flash column chromatography (silica gel, 20-25% EtOAc/hexanes) to provide methyl 4-amino-2-chloro-5-iodo-benzoate 70n as major the product and methyl 4-amino-2-chloro-3-iodo-benzoate 70o as the minor product.

Workup

  1. customThe resulting reaction mixture
  2. concentrationThe reaction mixture was concentrated
  3. custompartitioned between EtOAc and water
  4. concentrationThe organic layer was concentrated
  5. custompurified by flash column chromatography (silica gel, 20-25% EtOAc/hexanes)

Sources & evidence

ORD record
ord-4cd2accce769468caad1c8d5dde68b1b
Source dataset
uspto-grants-2013_12
Patent number
US08604017B2

Reaction notes

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