Bromine → 4-Amino-3,6-dichloro-5-bromopyridine-2-carboxylic acid

HRID 378781Notes

Reaction equation

HRID 378781 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([Cl:8])[N:5]=[C:4]([C:9]([O:11]C)=[O:10])[C:3]=1[Cl:13].[Br:14]Br>S(=O)(=O)(O)O>[NH2:1][C:2]1[C:7]([Br:14])=[C:6]([Cl:8])[N:5]=[C:4]([C:9]([OH:11])=[O:10])[C:3]=1[Cl:13]

Participants

4

Reactant 2

HCID 24408BromineHCID 22677331Methyl 4-amino-3,6-dichloropyridine-2-carboxylate

Product 1

HCID 216966414-Amino-3,6-dichloro-5-bromopyridine-2-carboxylic acidYield 91%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of methyl 4-amino-3,6-dichloropyridine-2-carboxylate (18 g, 81 mmol) in 100 mL fuming sulfuric acid was added bromine (15 mL, excess). The resulting mixture was heated to 70° C. for 30 min, then allowed to cool to room temperature. This material was poured into ice water (1000 mL) and extracted with EtOAc (4×500 mL). The combined organic extracts were dried (MgSO4), filtered and concentrated to yield a brown solid. The crude product was purified via reverse phase HPLC (50% acetonitrile/water) to give 21 g of 4-amino-3,6-dichloro-5-bromopyridine-2-carboxylic acid as a white solid (91% yield); mp 201-202° C.

Workup

  1. temperatureto cool to room temperature
  2. extractionextracted with EtOAc (4×500 mL)
  3. dry with materialThe combined organic extracts were dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto yield a brown solid
  7. customThe crude product was purified via reverse phase HPLC (50% acetonitrile/water)

Sources & evidence

ORD record
ord-4c0b2be60fed4f279874a56a8102edac
Source dataset
uspto-grants-2001_10
Patent number
US06297197B1

Reaction notes

Loading…