2-Amino-5-chlorobenzoic acid → 2-Amino-3-bromo-5-chlorobenzoic acid

HRID 610471Notes

Reaction equation

HRID 610471 reaction equation
[NH2:1][C:2]1[CH:10]=[CH:9][C:8]([Cl:11])=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[Br:12]Br>CC(O)=O>[NH2:1][C:2]1[C:10]([Br:12])=[CH:9][C:8]([Cl:11])=[CH:7][C:3]=1[C:4]([OH:6])=[O:5]

Participants

4

Reactant 2

HCID 124762-Amino-5-chlorobenzoic acidHCID 24408Bromine

Product 1

HCID 117799312-Amino-3-bromo-5-chlorobenzoic acidYield 80%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
15 °C

Procedure

To a solution of 200 g (1.05 mol) of 2-amino-5-chlorobenzoic acid in 3.4 L of HOAc at 15° C. was added dropwise 184 g (1.15 mol) of Br2. The mixture was stirred at 15° C. for 4 hrs, quenched slowly into 8 L of water, and extracted with 2×2 L of t-BuOMe. The combined extract was washed with water, dried over MgSO4 and concentrated. The crude product was treated with hot hexane, filtered and dried to give 210 g (80%) of 2-amino-3-bromo-5-chlorobenzoic acid as white solid. Mp. 225-2280° C. 1H NMR (DMSO-d6): δ7.70 (d, J=2.6 Hz, 1 H), 7.69 (d, J=2.6 Hz, 1 H), 6.8 (bs, 2 H). 13C NMR (DMSO-d6): δ168.16, 147.06, 136.25, 130.19, 118.22, 112.35,110.34. IR:3480 (m), 3350 (m), 2920 (s), 1670 (s) cm-1. Analysis calcd. for C7H5BrClNO2 : C, 33.53, H, 2.00, N, 5.59; Found: C, 33.63, H, 2.12, N, 5.70. ##STR22##

Workup

  1. customquenched slowly into 8 L of water
  2. extractionextracted with 2×2 L of t-BuOMe
  3. extractionThe combined extract
  4. washwas washed with water
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. additionThe crude product was treated with hot hexane
  8. filtrationfiltered
  9. customdried

Sources & evidence

ORD record
ord-56f61c2643744556b13e83e21a40d69f
Source dataset
uspto-grants-1999_12
Patent number
US05998620

Reaction notes

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