Sulfuric Acid → Methyl 3-amino-6-bromopyridine-2-carboxylate

HRID 1469094Notes

Reaction equation

HRID 1469094 reaction equation
[NH2:1][C:2]1[C:3]([C:8]([O:10][CH3:11])=[O:9])=[N:4][CH:5]=[CH:6][CH:7]=1.S(=O)(=O)(O)O.[Br:17]Br>O>[NH2:1][C:2]1[C:3]([C:8]([O:10][CH3:11])=[O:9])=[N:4][C:5]([Br:17])=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 24408BromineHCID 9898880Methyl 3-aminopicolinate

Product 1

HCID 45480453Methyl 3-amino-6-bromopyridine-2-carboxylateYield 50%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

20 g of methyl 3-aminopyridine-2-carboxylate are suspended in 120 ml of water in a flask. After addition of 100 ml of sulfuric acid (2 mol/l), the mixture is cooled to 0° C., 6.73 ml of bromine are added dropwise, and the mixture is stirred at 25° C. until the acid has reacted completely (HPLC check, about 24 hours). A precipitate precipitates out of the reaction solution. This is filtered off, dissolved in EA, washed with sodium thiosulfate solution, the organic phase is dried and purified by means of column chromatography (gradient heptane: EA 5-100% in 30 min.), giving 15 g of methyl 3-amino-6-bromo-pyridine-2-carboxylate as red-brown solid (yield 50%, content 98%); MS-FAB (M+H+)=232.9; Rf (polar method): 1.518 min.

Workup

  1. customhas reacted completely (HPLC check, about 24 hours)
  2. customA precipitate precipitates out of the reaction solution
  3. filtrationThis is filtered off
  4. dissolutiondissolved in EA
  5. washwashed with sodium thiosulfate solution
  6. customthe organic phase is dried
  7. custompurified by means of column chromatography (gradient heptane: EA 5-100% in 30 min.)

Sources & evidence

ORD record
ord-0ccecf2f4154478a8c6ded5295830197
Source dataset
uspto-grants-2015_04
Patent number
US09006255B2

Reaction notes

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