Acetic Acid → 3-Chloro-4,5-difluoroanthranilic acid

HRID 729402Notes

Reaction equation

HRID 729402 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([NH2:12])[C:5](=[CH:9][C:10]=1[F:11])[C:6]([OH:8])=[O:7].C(O)(=O)C.C(O[Cl:22])(C)(C)C>ClCCl.C(OCC)(=O)C>[Cl:22][C:3]1[C:2]([F:1])=[C:10]([F:11])[CH:9]=[C:5]([C:6]([OH:8])=[O:7])[C:4]=1[NH2:12]

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 521297Tert-Butyl hypochloriteHCID 7359652-Amino-4,5-difluorobenzoic acid

Product 1

HCID 219789243-Chloro-4,5-difluoroanthranilic acidYield 100.8%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 4,5-difluoroanthranilic acid (2.45 g, 14.2 mmol) in dichloromethane (25 mL) is added acetic acid (10 mL) and hypochlorous acid tert-butyl ester (1.75 mL, 15.6 mmol). After 2 hours, the reaction mixture is diluted with ethyl acetate and washed with water and brine. The organic layer is dried over MgSO4, filtered, and concentrated. The resulting residue is purified via flash column chromatography (5% isopropyl alcohol/1% formic acid/94% dichloromethane) to afford 3-chloro-4,5-difluoroanthranilic acid as an oil (2.97 g). MS CI: m/z 206 (M+).

Workup

  1. washwashed with water and brine
  2. dry with materialThe organic layer is dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe resulting residue is purified via flash column chromatography (5% isopropyl alcohol/1% formic acid/94% dichloromethane)

Sources & evidence

ORD record
ord-a6349ee83f574578aabef6e2f15d5669
Source dataset
uspto-grants-2009_09
Patent number
US07582627B2

Reaction notes

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