2,2'-Bipyridine → (E)-ethyl 4-(3-(3,5-dichlorophenyl)-4,4,4-trifluorobut-1-enyl)-2-methylbenzoate

HRID 587667Notes

Reaction equation

HRID 587667 reaction equation
[CH3:1][C:2]1[CH:12]=[C:11]([CH:13]=[CH2:14])[CH:10]=[CH:9][C:3]=1[C:4]([O:6][CH2:7][CH3:8])=[O:5].Br[CH:16]([C:21]1[CH:26]=[C:25]([Cl:27])[CH:24]=[C:23]([Cl:28])[CH:22]=1)[C:17]([F:20])([F:19])[F:18].N1C=CC=CC=1C1C=CC=CN=1>ClC1C=CC=CC=1Cl.Cl[Cu]>[Cl:27][C:25]1[CH:26]=[C:21]([CH:16]([C:17]([F:20])([F:18])[F:19])/[CH:14]=[CH:13]/[C:11]2[CH:10]=[CH:9][C:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])=[C:2]([CH3:1])[CH:12]=2)[CH:22]=[C:23]([Cl:28])[CH:24]=1

Participants

6

Reactant 3

HCID 14742,2'-BipyridineHCID 58390837Ethyl 2-methyl-4-vinylbenzoateHCID 866751181-(1-Bromo-2,2,2-trifluoroethyl)-3,5-dichlorobenzene

Product 1

HCID 86675123(E)-ethyl 4-(3-(3,5-dichlorophenyl)-4,4,4-trifluorobut-1-enyl)-2-methylbenzoateYield 40%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 72391,2-DichlorobenzeneSolvent

Conditions

Temperature
180 °C

Procedure

To a stirred solution of ethyl 2-methyl-4-vinylbenzoate (2.0 g, 10.5 mmol) in 1,2-dichlorobenzene (25 mL) were added 1-(1-bromo-2,2,2-trifluoroethyl)-3,5-dichlorobenzene (6.44 g, 21.0 mmol), CuCl (208 mg, 21 mmol) and 2,2bipyridyl (0.65 g, 4.1 mmol). The 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 25° C. and filtered, and the filtrate was concentrated under reduced pressure. Purification by flash chromatography (SiO2, 100-200 mesh; eluting with 25-30% EtOAc in petroleum ether) afforded the title compound as a solid (1.7 g, 40%): 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J =8.0 Hz, 1H), 7.37 (m, 1H), 7.27-7.24 (m, 4H), 6.59 (d, J=16.0 Hz, 1H), 6.59 (dd, J=16.0, 8.0 Hz, 1H), 4.38 (q, J=7.2 Hz, 2H), 4.08 (m, 1H), 2.62 (s, 3H), 1.42 (t, J=7.2 Hz, 3H); ESIMS m/z 415.06 ([M−H]−); IR (thin film) 1717, 1255, 1114 cm−1.

Workup

  1. customThe reaction mixture was degassed with argon for 30 min
  2. temperaturethe reaction mixture was cooled to 25° C.
  3. filtrationfiltered
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customPurification
  6. washby flash chromatography (SiO2, 100-200 mesh; eluting with 25-30% EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-24131f4e87ea477888061b2f017277e4
Source dataset
uspto-grants-2016_01
Patent number
US09226501B2

Reaction notes

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