Sodium Bicarbonate → 5-Bromo-2-methyl-3-nitropyridine

HRID 1892588Notes

Reaction equation

HRID 1892588 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N+:19]([O-:21])=[O:20])[C:5]([CH:8](C(OCC)=O)C(OCC)=O)=[N:6][CH:7]=1.C(=O)(O)[O-].[Na+]>Cl>[Br:1][C:2]1[CH:3]=[C:4]([N+:19]([O-:21])=[O:20])[C:5]([CH3:8])=[N:6][CH:7]=1

Participants

4

Reactant 2

HCID 516892Sodium BicarbonateHCID 57516275Diethyl 2-(5-bromo-3-nitropyridin-2-yl)malonate

Product 1

HCID 250672665-Bromo-2-methyl-3-nitropyridineYield 72.6%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

A mixture of the diethyl 2-(5-bromo-3-nitropyridin-2-yl)malonate (31.8 g, 88 mmol) in aqueous hydrochloric acid (6M, 1.4 L) was stirred at reflux for 18 hours. The reaction mixture was cooled to ambient temperature and added very slowly to a saturated aqueous solution of aqueous sodium bicarbonate (4 L) at 0° C. The mixture was then extracted with dichloromethane (7 L), dried over magnesium sulfate and the solvent removed in vacuo to give 5-bromo-2-methyl-3-nitropyridine as an orange oil (13.8 g, 63.9 mmol, 72%) which solidified upon standing, 1HNMR (300 MHz, CDCl3): δ ppm 8.78 (s, 1H), 8.43 (s, 1H), 2.79 (s, 3H).

Workup

  1. temperatureat reflux for 18 hours
  2. extractionThe mixture was then extracted with dichloromethane (7 L)
  3. dry with materialdried over magnesium sulfate
  4. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-40f31ea47c004d2387093a5a7ce7d38e
Source dataset
uspto-grants-2013_08
Patent number
US08507681B2

Reaction notes

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