2,2'-Bipyridine → (E)-2-(3-nitro-1H-1,2,4-triazol-1-yl)-5-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-enyl)benzonitrile

HRID 587287Notes

Reaction equation

HRID 587287 reaction equation
[N+:1]([C:4]1[N:8]=[CH:7][N:6]([C:9]2[CH:16]=[CH:15][C:14]([CH:17]=[CH2:18])=[CH:13][C:10]=2[C:11]#[N:12])[N:5]=1)([O-:3])=[O:2].Br[CH:20]([C:25]1[CH:26]=[C:27]([Cl:33])[C:28]([Cl:32])=[C:29]([Cl:31])[CH:30]=1)[C:21]([F:24])([F:23])[F:22].N1C=CC=CC=1C1C=CC=CN=1>ClC1C=CC=CC=1Cl.Cl[Cu]>[N+:1]([C:4]1[N:8]=[CH:7][N:6]([C:9]2[CH:16]=[CH:15][C:14](/[CH:17]=[CH:18]/[CH:20]([C:25]3[CH:26]=[C:27]([Cl:33])[C:28]([Cl:32])=[C:29]([Cl:31])[CH:30]=3)[C:21]([F:23])([F:22])[F:24])=[CH:13][C:10]=2[C:11]#[N:12])[N:5]=1)([O-:3])=[O:2]

Participants

6

Reactant 3

HCID 14742,2'-BipyridineHCID 866751531-(1-Bromo-2,2,2-trifluoroethyl)-3,4,5-trichlorobenzeneHCID 866752162-(3-nitro-1H-1,2,4-triazol-1-yl)-5-vinylbenzonitrile

Product 1

HCID 86675224(E)-2-(3-nitro-1H-1,2,4-triazol-1-yl)-5-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-enyl)benzonitrile

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 72391,2-DichlorobenzeneSolvent

Conditions

Temperature
180 °C

Procedure

To a stirred solution of 2-(3-nitro-1H-1,2,4-triazol-1-yl)-5-vinylbenzonitrile (0.9 g, 3.7 mmol) in 1,2-dichlorobenzene (10 mL), were added 5-(1-bromo-2,2,2-trifluoroethyl)-1,2,3-trichlorobenzene (2.5 g, 7.5 mmol), CuCl (73 mg, 0.74 mmol) and 2,2-bipyridyl (0.23 g, 1.49 mmol) and the resultant reaction mixture was degassed with argon for 30 min and then stirred at 180° C. for 14 h. After completion of the reaction (TLC), the reaction mixture was cooled to ambient temperature and filtered and the filtrate was concentrated under reduced pressure. Purification by flash chromatography (SiO2, 100-200 mesh, 25-30% EtOAc in Pet ether) afforded the title compound as a off white solid (0.9 g, 50%): mp 70-73° C.; 1H NMR (300 MHz, CDCl3) δ 8.86 (s, 1H), 7.88 (m, 3H), 7.44 (s, 2H), 6.67 (d, J=16.0 Hz, 1H), 6.56 (dd, J=16.0, 7.6 Hz, 1H), 4.19 (m, 1H); ESIMS m/z 436.11 ([M−2H]−).

Workup

  1. customthe resultant reaction mixture
  2. customwas degassed with argon for 30 min
  3. customAfter completion of the reaction (TLC)
  4. temperaturethe reaction mixture was cooled to ambient temperature
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated under reduced pressure
  7. customPurification by flash chromatography (SiO2, 100-200 mesh, 25-30% EtOAc in Pet ether)

Sources & evidence

ORD record
ord-6fd736409add407fa76486a589c61c87
Source dataset
uspto-grants-2016_01
Patent number
US09226500B2

Reaction notes

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