2,2'-Bipyridine → (E)-N-(2-chloro-4-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzyl)pyridin-2-amine

HRID 1502746Notes

Reaction equation

HRID 1502746 reaction equation
[Cl:1][C:2]1[CH:15]=[C:14]([CH:16]=[CH2:17])[CH:13]=[CH:12][C:3]=1[CH2:4][NH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][N:7]=1.Br[CH:19]([C:24]1[CH:25]=[C:26]([Cl:32])[C:27]([Cl:31])=[C:28]([Cl:30])[CH:29]=1)[C:20]([F:23])([F:22])[F:21].N1C=CC=CC=1C1C=CC=CN=1>ClC1C=CC=CC=1Cl.Cl[Cu]>[Cl:1][C:2]1[CH:15]=[C:14](/[CH:16]=[CH:17]/[CH:19]([C:24]2[CH:25]=[C:26]([Cl:32])[C:27]([Cl:31])=[C:28]([Cl:30])[CH:29]=2)[C:20]([F:22])([F:21])[F:23])[CH:13]=[CH:12][C:3]=1[CH2:4][NH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][N:7]=1

Participants

6

Reactant 3

HCID 14742,2'-BipyridineHCID 866751531-(1-Bromo-2,2,2-trifluoroethyl)-3,4,5-trichlorobenzeneHCID 86675183N-(2-chloro-4-vinylbenzyl)pyridin-2-amine

Product 1

HCID 86675208(E)-N-(2-chloro-4-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzyl)pyridin-2-amineYield 35%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 72391,2-DichlorobenzeneSolvent

Conditions

Temperature
180 °C

Procedure

To a stirred solution of N-(2-chloro-4-vinylbenzyl)pyridin-2-amine (0.3 g, 1.22 mmol) in 1,2-dichlorobenzene (5 mL) were added 5-(1-bromo-2,2,2-trifluoroethyl)-1,2,3-trichlorobenzene (0.83 g, 2.44 mmol), CuCl (24 mg, 0.24 mmol) and 2,2-bipyridyl (76 mg, 0.48 mmol). The resultant reaction mixture was degassed with argon for 30 min and then stirred at 180° C. for 24 h. After the reaction was deemed complete by 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; 15% EtOAc in n-hexane) afforded the title compound as an off-white solid (0.2 g, 35%): mp 140-142° C.; 1H NMR (400 MHz, CDCl3) δ 8.11 (d, J=4.0 Hz, 1H), 7.40 (m, 5H), 7.22 (m, 1H), 6.61 (m, 2H), 6.35 (m, 2H), 4.94 (br s, 1H), 4.61 (d, J=6.4 Hz, 2H), 4.11 (m, 1H); ESIMS m/z 505.39 ([M+H]+).

Workup

  1. customThe resultant reaction mixture
  2. customwas degassed with argon for 30 min
  3. temperaturethe reaction mixture was cooled to ambient temperature
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. customPurification by flash chromatography (SiO2, 100-200 mesh; 15% EtOAc in n-hexane)

Sources & evidence

ORD record
ord-6bccf7601ff043d8a0ec3acc8b89b845
Source dataset
uspto-grants-2015_12
Patent number
US09210927B2

Reaction notes

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