4-Azido-5-bromo-2-(2,4-dichlorophenylamino)-3-fluorobenzoic acid methyl ester → 4-Amino-5-bromo-2-(2,4-dichlorophenylamino)-3-fluorobenzoic acid methyl ester

HRID 500560Notes

Reaction equation

HRID 500560 reaction equation
[CH3:1][O:2][C:3](=[O:24])[C:4]1[CH:9]=[C:8]([Br:10])[C:7]([N:11]=[N+]=[N-])=[C:6]([F:14])[C:5]=1[NH:15][C:16]1[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][C:17]=1[Cl:23]>CC(O)=O.C(Cl)Cl.C(Cl)Cl.[Zn]>[CH3:1][O:2][C:3](=[O:24])[C:4]1[CH:9]=[C:8]([Br:10])[C:7]([NH2:11])=[C:6]([F:14])[C:5]=1[NH:15][C:16]1[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][C:17]=1[Cl:23]

Participants

5

Reactant 1

HCID 865986364-Azido-5-bromo-2-(2,4-dichlorophenylamino)-3-fluorobenzoic acid methyl ester

Product 1

HCID 865986354-Amino-5-bromo-2-(2,4-dichlorophenylamino)-3-fluorobenzoic acid methyl esterYield 64.4%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 6344DichloromethaneSolventHCID 21922555Acetic acid methylene chlorideSolvent

Procedure

To a mixture of 4-azido-5-bromo-2-(2,4-dichlorophenylamino)-3-fluorobenzoic acid methyl ester (2.05 g, 4.72 mmol) in AcOH-CH2Cl2 (10-30 mL) was added Zn dust (1.59 g, 24.3 mmol) at 0° C. The reaction mixture was warmed to room temperature. The resulting mixture was stirred for 1 hour. The reaction mixture was diluted with CH2Cl2, and washed with water, saturated aqueous NaHCO3 (2×), water, and brine. The organic layer was dried over MgSO4, filtered, and concentrated in vacuo to give the crude material which was purified by silica gel flash column chromatography(3 to 5% EtOAc in hexanes) to afford the desired product (1.24 g, 64%).

Workup

  1. washwashed with water, saturated aqueous NaHCO3 (2×), water, and brine
  2. dry with materialThe organic layer was dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customto give the crude material which
  6. customwas purified by silica gel flash column chromatography(3 to 5% EtOAc in hexanes)

Sources & evidence

ORD record
ord-71e8096aeaf44d5097f42a7a866d0f7b
Source dataset
uspto-grants-2010_08
Patent number
US07772234B2

Reaction notes

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