Ethyl Acetate → Methyl 4-(2-amino-5-bromopyridin-3-ylthio)benzoate

HRID 911865Notes

Reaction equation

HRID 911865 reaction equation
[NH2:1][C:2]1[C:7]([S:8][C:9]2[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][CH:10]=2)=[CH:6][CH:5]=[CH:4][N:3]=1.[Br:19]Br.S(=O)(O)[O-].[Na+].C(OCC)(=O)C>C(O)(=O)C>[NH2:1][C:2]1[C:7]([S:8][C:9]2[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][CH:10]=2)=[CH:6][C:5]([Br:19])=[CH:4][N:3]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 24408BromineHCID 23665763Sodium BisulfiteHCID 66994709Methyl 4-(2-aminopyridin-3-ylthio)benzoate

Product 1

HCID 66994425Methyl 4-(2-amino-5-bromopyridin-3-ylthio)benzoateYield 68%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
0 °C

Procedure

Placed methyl 4-(2-aminopyridin-3-ylthio)benzoate (5.50 g, 21.1 mmol) in acetic acid (25 mL) and cooled to 0° C. Slowly added bromine (1.35 mL, 26.4 mmol) and stirred for an hour. Poured reaction mixture onto saturated sodium bisulfite and ice. Extracted with dichloromethane three times, washed with 2N NaOH, water, brine, dried, and concentrated. Subjected to MPLC (Biotage) eluting with 3:2 hexane:ethyl acetate to afford the title compound (4.87 g, 68.0% yield).

Workup

  1. additionPoured
  2. extractionExtracted with dichloromethane three times
  3. washwashed with 2N NaOH, water, brine
  4. customdried
  5. concentrationconcentrated
  6. washeluting with 3:2 hexane

Sources & evidence

ORD record
ord-d74b4ae2553249d68ef4e6d3e6552608
Source dataset
uspto-grants-2011_09
Patent number
US08022223B2

Reaction notes

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