2-Amino-4-methylpyridine → 2-Amino-5-bromo-4-methylpyridine

HRID 2265154Notes

Reaction equation

HRID 2265154 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][N:3]=1.[BrH:9].[NH+]1C=CC=CC=1.S([O-])([O-])=O.[Na+].[Na+]>O1CCCC1>[NH2:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([Br:9])=[CH:4][N:3]=1

Participants

5

Reactant 3

HCID 15332-Amino-4-methylpyridineHCID 24437Sodium SulfiteHCID 21226041Pyridinium hydrobromide

Product 1

HCID 8176952-Amino-5-bromo-4-methylpyridineYield 53.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

In a nitrogen atmosphere, 1.08 g of 2-amino-4-methylpyridine was dissolved in 75 mL of tetrahydrofuran, and tetrahydrofuran (75 mL) solution of 3.20 g of pyridinium hydrobromide perbromide was dropwise added thereto at room temperature, over 1.5 hours. After the addition, this was stirred at room temperature for 40 minutes, and 100 mL of aqueous saturated sodium sulfite solution was added to the reaction mixture. This was extracted with ethyl acetate, and the ethyl acetate layer was dried with magnesium sulfate. The solvent was evaporated off under reduced pressure, and the residue was separated and purified through silica gel column chromatography (hexane/ethyl acetate=4/1 to ethyl acetate) to obtain 1.00 g of the entitled compound as a white solid.

Workup

  1. additionAfter the addition
  2. extractionThis was extracted with ethyl acetate
  3. dry with materialthe ethyl acetate layer was dried with magnesium sulfate
  4. customThe solvent was evaporated off under reduced pressure
  5. customthe residue was separated
  6. custompurified through silica gel column chromatography (hexane/ethyl acetate=4/1 to ethyl acetate)

Sources & evidence

ORD record
ord-1f01f493708f42c2b5f93d1f57d3ee6c
Source dataset
uspto-grants-2010_12
Patent number
US07855294B2

Reaction notes

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