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

HRID 401729Notes

Reaction equation

HRID 401729 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]Cl>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 10112Calcium CarbonateHCID 24640Iodine chlorideHCID 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 monochloride (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-c08078a2fcfe4527bdb257392bca5599
Source dataset
uspto-grants-2014_06
Patent number
US08741887B2

Reaction notes

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