1,10-Phenanthroline hydrate → 7-Bromo-2-phenyl-[1,2,4]triazolo[1,5-A]pyridine

HRID 517645Notes

Reaction equation

HRID 517645 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([Br:8])[CH:5]=[CH:4][N:3]=1.O.N1[C:23]2[C:14](=[CH:15][CH:16]=[C:17]3[C:22]=2N=CC=C3)[CH:13]=CC=1.O=O.[N:26]#N>[Cu]Br.C(#N)C1C=CC=CC=1>[Br:8][C:6]1[CH:5]=[CH:4][N:3]2[N:26]=[C:13]([C:14]3[CH:23]=[CH:22][CH:17]=[CH:16][CH:15]=3)[N:1]=[C:2]2[CH:7]=1

Participants

6

Reactant 3

HCID 212261,10-Phenanthroline hydrateHCID 114954NitroxHCID 6932822-Amino-4-bromopyridine

Product 1

HCID 677755007-Bromo-2-phenyl-[1,2,4]triazolo[1,5-A]pyridineYield 78%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 7505BenzonitrileSolvent

Conditions

Temperature
130 °C

Procedure

A mixture of 2-amino-4-bromopyridine (100.0 g, 0.566 mol), copper (I) bromide (4.15 g, 28.3 mmol), 1,10-phenanthroline monohydrate (5.67 g, 28.3 mmol) and benzonitrile (600 mL) was heated in a 1.5-L autoclave to 130° C. and stirred for 23 h under a continuous gas flow (O2/N2 8:92) of 200 mL/min (constant pressure: 20 bar). After the autoclave was vented and opened (100% conversion, GC method cf. example 1.8), the dark brown reaction suspension was cooled to 0-5° C. and filtered. The filter cake was washed with MeOH (600 mL) and dried to yield crude 7-bromo-2-phenyl-[1,2,4]triazolo[1,5-a]pyridine (120.6 g, 78%) as a green solid with 100% purity (HPLC area-%, GC method cf. example 1.8).

Workup

  1. temperaturethe dark brown reaction suspension was cooled to 0-5° C.
  2. filtrationfiltered
  3. washThe filter cake was washed with MeOH (600 mL)
  4. customdried

Sources & evidence

ORD record
ord-abe85169dec34f2a9656de9aab35e048
Source dataset
uspto-grants-2015_08
Patent number
US09115130B2

Reaction notes

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