2,2'-Bipyridine → (E)-2-(2-chloro-4-(3-(3,5-dichlorophenyl)-4,4,4-trifluorobut-1-en-1-yl)benzyl)isoindoline-1,3-dione

HRID 587240Notes

Reaction equation

HRID 587240 reaction equation
[Cl:1][C:2]1[CH:19]=[C:18]([CH:20]=[CH2:21])[CH:17]=[CH:16][C:3]=1[CH2:4][N:5]1[C:13](=[O:14])[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6]1=[O:15].Br[CH:23]([C:28]1[CH:33]=[C:32]([Cl:34])[CH:31]=[C:30]([Cl:35])[CH:29]=1)[C:24]([F:27])([F:26])[F:25].N1C=CC=CC=1C1C=CC=CN=1>ClC1C=CC=CC=1Cl.Cl[Cu]>[Cl:1][C:2]1[CH:19]=[C:18](/[CH:20]=[CH:21]/[CH:23]([C:28]2[CH:29]=[C:30]([Cl:35])[CH:31]=[C:32]([Cl:34])[CH:33]=2)[C:24]([F:27])([F:26])[F:25])[CH:17]=[CH:16][C:3]=1[CH2:4][N:5]1[C:13](=[O:14])[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6]1=[O:15]

Participants

6

Reactant 3

HCID 14742,2'-BipyridineHCID 866751181-(1-Bromo-2,2,2-trifluoroethyl)-3,5-dichlorobenzeneHCID 866751792-(2-Chloro-4-vinylbenzyl)isoindoline-1,3-dione

Product 1

HCID 86675180(E)-2-(2-chloro-4-(3-(3,5-dichlorophenyl)-4,4,4-trifluorobut-1-en-1-yl)benzyl)isoindoline-1,3-dioneYield 50%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 72391,2-DichlorobenzeneSolvent

Conditions

Temperature
180 °C

Procedure

To a stirred solution of 2-(2-chloro-4-vinylbenzyl)isoindoline-1,3-dione (2.0 g, 6.51 mmol) in 1,2-dichlorobenzene (25 mL) were added 1-(1-bromo-2,2,2-trifluoroethyl)-3,5-dichlorobenzene (3.48 g, 11.36 mmol), CuCl (112 mg, 1.13 mmol) and 2,2-bipyridyl (0.35 g). The resultant reaction mixture was degassed with argon for 30 min and then was 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. The residue was purified by flash chromatography (SiO2, 100-200 mesh; 25-30% EtOAc in n-hexane) to afford the title compound as solid (1.3 g, 50%): mp 141-143° C.; 1H NMR (400 MHz, CDCl3) δ 7.92 (m, 2H), 7.79 (m, 2H), 7.42 (m, 2H), 7.24 (m, 2H), 7.20 (m, 2H), 6.54 (d, J=16.0 Hz, 1H), 6.34 (dd, J=16.0, 8.0 Hz, 1H), 5.00 (s, 2H), 4.10 (m, 1H); ESIMS m/z 524.07 ([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. customThe residue was purified by flash chromatography (SiO2, 100-200 mesh; 25-30% EtOAc in n-hexane)

Sources & evidence

ORD record
ord-8fb96009716a422e815bbf2fa43d3eb2
Source dataset
uspto-grants-2016_01
Patent number
US09226500B2

Reaction notes

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