Hydrogen Bromide → 3-Bromo-5-(trifluoromethyl)pyridine

HRID 1261666Notes

Reaction equation

HRID 1261666 reaction equation
N([O-])=O.[Na+].[F:5][C:6]([F:15])([F:14])[C:7]1[CH:8]=[C:9](N)[CH:10]=[N:11][CH:12]=1.[BrH:16]>O.C(Cl)Cl.[Cu]Br>[Br:16][C:9]1[CH:10]=[N:11][CH:12]=[C:7]([C:6]([F:15])([F:14])[F:5])[CH:8]=1

Participants

7

Reactant 3

HCID 260Hydrogen Bromide2×HCID 140519365-(Trifluoromethyl)pyridin-3-amineHCID 23668193Sodium Nitrite

Product 1

HCID 111279913-Bromo-5-(trifluoromethyl)pyridine

Reagents, catalysts & solvents 3

HCID 24593copper(I) bromideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
60 °C

Procedure

A solution of sodium nitrite (402 mg, 5.83 mmol) in water (6.8 mL) was added slowly to a suspension of 5-(trifluoromethyl)pyridin-3-amine (947 mg, 5.55 mmol) in hydrogen bromide (48% aqueous solution, 1.57 mL) in ice-water bath. After being stirred for 10 min, the resulting orange diazo solution was directly but slowly transferred to a stirring mixture of copper(I) bromide (876 mg, 6.11 mmol) and hydrogen bromide (48% aqueous solution, 0.38 mL). The resulting brown mixture was heated at 60° C. for 1 h. After cooling to room temperature, the mixture was diluted with methylene chloride, washed with 50% NaOH (until pH=11), and water. The aqueous layer was back extracted with methylene chloride. The combined organic extracts were carefully concentrated under vacuum to provide crude product without purification.

Workup

  1. temperatureAfter cooling to room temperature
  2. washwashed with 50% NaOH (until pH=11), and water
  3. extractionThe aqueous layer was back extracted with methylene chloride
  4. concentrationThe combined organic extracts were carefully concentrated under vacuum
  5. customto provide crude product
  6. customwithout purification

Sources & evidence

ORD record
ord-54d5caac30f34704922c8434d13d86b8
Source dataset
uspto-grants-2013_06
Patent number
US08470827B2

Reaction notes

Loading…