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

HRID 473598Notes

Reaction equation

HRID 473598 reaction equation
[NH2:1][C:2]1[C:11]([I:12])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([Cl:13])[CH:3]=1.C([O-])([O-])=O.[Ca+2].II.[CH2:21]([Cl:23])Cl>CO>[NH2:1][C:2]1[C:11]([I:12])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([Cl:13])[CH:3]=1.[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:21]([Cl:23])[C:11]=1[I:12]

Participants

7

Reactant 4

HCID 807IodineHCID 6344DichloromethaneHCID 10112Calcium CarbonateHCID 11839203Benzoic acid, 4-amino-2-chloro-5-iodo-, methyl ester2×

Product 2

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

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Methyl 4-amino-2-chloro-5-iodo-benzoate, 23c. To a suspension of compound 23b (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 23c as the major the product and methyl 4-amino-2-chloro-3-iodo-benzoate 23d 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-8a3a17118cb648b28cd49bbc5fa6d531
Source dataset
uspto-grants-2014_01
Patent number
US08637498B2

Reaction notes

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