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 587758Notes

Reaction equation

HRID 587758 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 an 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−H]−).

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-5a13f4f0b68b4365acee8b8a6ca5fdd2
Source dataset
uspto-grants-2016_01
Patent number
US09226501B2

Reaction notes

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