Hydrochloric Acid → 2-Bromo-6-chloro-4-methylpyridine

HRID 725758Notes

Reaction equation

HRID 725758 reaction equation
N[C:2]1[N:7]=[C:6]([Br:8])[CH:5]=[C:4]([CH3:9])[CH:3]=1.N([O-])=O.[Na+].[OH-].[Na+].[ClH:16]>O>[Br:8][C:6]1[CH:5]=[C:4]([CH3:9])[CH:3]=[C:2]([Cl:16])[N:7]=1

Participants

6

Reactant 4

HCID 313Hydrochloric Acid2×HCID 14798Sodium HydroxideHCID 221765076-Bromo-4-methylpyridin-2-amineHCID 23668193Sodium Nitrite

Product 1

HCID 111172342-Bromo-6-chloro-4-methylpyridineYield 40%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
-50 °C

Procedure

A solution of 56 g 6-amino-2-bromo-4-methylpyridine in 500 ml of concentrated hydrochloric acid was cooled to -50° C. and saturated with gaseous HCl via a gas inlet. Under continuous cooling a solution of 25 g sodium nitrite in 60 ml water was added slowly. The reaction mixture was stirred for a further 2 hours at -50° C. The mixture was allowed to warm up to ambient temperature and set alkaline with a 50% aqueous solution of sodium hydroxide. The aqueous phase was extracted three times each with 200 ml dichloromethane. The combined extracts were dried with calcium chloride, and the solvent removed in vacuo to afford 22.5 g (40%) of 2-bromo-6-chloro-4-methylpyridine as a pale brown solid of melting point 76° C.

Workup

  1. additionwas added slowly
  2. temperatureto warm up to ambient temperature
  3. extractionThe aqueous phase was extracted three times each with 200 ml dichloromethane
  4. dry with materialThe combined extracts were dried with calcium chloride
  5. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-70bce3b07276442ba5e721cc05104701
Source dataset
uspto-grants-1998_01
Patent number
US05707932

Reaction notes

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