Hydrogen Bromide → 2-Bromo-4-tert-butylpyridine

HRID 1910353Notes

Reaction equation

HRID 1910353 reaction equation
N[C:2]1[CH:7]=[C:6]([C:8]([CH3:11])([CH3:10])[CH3:9])[CH:5]=[CH:4][N:3]=1.[BrH:12].BrBr.N([O-])=O.[Na+].[OH-].[Na+]>O.C(OCC)(=O)C>[Br:12][C:2]1[CH:7]=[C:6]([C:8]([CH3:11])([CH3:10])[CH3:9])[CH:5]=[CH:4][N:3]=1

Participants

8

Reactant 5

HCID 260Hydrogen BromideHCID 14798Sodium HydroxideHCID 24408BromineHCID 123519414-(tert-Butyl)pyridin-2-amineHCID 23668193Sodium Nitrite2×

Product 1

HCID 131833052-Bromo-4-tert-butylpyridineYield 85%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

39.0 g (0.26 mol) of 2-amino-4-tert-butyl-pyridine was added with ˜100 mL of 60% HBr, then stirred at −10° C. to −17° C. 124.0 g (0.78 mol) of pre-cooled Br2 (˜0° C.) was added dropwise added and the mixture was stirred for 20 mins. Pre-cooled (0° C.) NaNO2 solution of 46.0 g (0.67 mol) of NaNO2 dissolved in ˜80 mL of water was added dropwise into the reaction mixture at −10° C. to −17° C. After addition, the reaction was stirred for one hour. Ice-cooled ˜25% NaOH solution was added slowly until the solution became basic. 200 mL of ethyl acetate was added to the mixture to extract the organic phase. The organic phase solvent was evaporated and distilled under vacuum. ˜47 g (85% yield) of 2-bromo-4-tert-butyl-pyridine was obtained. The product was confirmed by MS.

Workup

  1. additionadded
  2. stirringthe mixture was stirred for 20 mins
  3. additionwas added dropwise into the reaction mixture at −10° C. to −17° C
  4. additionAfter addition
  5. stirringthe reaction was stirred for one hour
  6. additionwas added slowly until the solution
  7. extractionto extract the organic phase
  8. customThe organic phase solvent was evaporated
  9. distillationdistilled under vacuum

Sources & evidence

ORD record
ord-a14dd41791f041a9a48ea78f7fdccf4c
Source dataset
uspto-grants-2013_12
Patent number
US08603645B2

Reaction notes

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