Cesium carbonate → Perfluorophenyl 1-(4'-chloro-2-fluoro-3',5-dimethyl-[1,1'-biphenyl]-4-yl)-2-oxo-1,2-dihydroquinoline-6-sulfonate

HRID 1504384Notes

Reaction equation

HRID 1504384 reaction equation
Br[C:2]1[C:7]([F:8])=[CH:6][C:5]([N:9]2[C:18]3[C:13](=[CH:14][C:15]([S:19]([O:22][C:23]4[C:28]([F:29])=[C:27]([F:30])[C:26]([F:31])=[C:25]([F:32])[C:24]=4[F:33])(=[O:21])=[O:20])=[CH:16][CH:17]=3)[CH:12]=[CH:11][C:10]2=[O:34])=[C:4]([CH3:35])[CH:3]=1.[Cl:36][C:37]1[CH:42]=[CH:41][C:40](B(O)O)=[CH:39][C:38]=1[CH3:46].C(=O)([O-])[O-].[Cs+].[Cs+]>[Cu]Cl>[Cl:36][C:37]1[CH:42]=[CH:41][C:40]([C:2]2[CH:3]=[C:4]([CH3:35])[C:5]([N:9]3[C:18]4[C:13](=[CH:14][C:15]([S:19]([O:22][C:23]5[C:28]([F:29])=[C:27]([F:30])[C:26]([F:31])=[C:25]([F:32])[C:24]=5[F:33])(=[O:21])=[O:20])=[CH:16][CH:17]=4)[CH:12]=[CH:11][C:10]3=[O:34])=[CH:6][C:7]=2[F:8])=[CH:39][C:38]=1[CH3:46]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 3786632(4-Chloro-3-methylphenyl)boronic acidHCID 117736966Perfluorophenyl 1-(4-bromo-5-fluoro-2-methylphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate

Product 1

HCID 117737061Perfluorophenyl 1-(4'-chloro-2-fluoro-3',5-dimethyl-[1,1'-biphenyl]-4-yl)-2-oxo-1,2-dihydroquinoline-6-sulfonateYield 78%

Reagents, catalysts & solvents 1

HCID 62652Cuprous chlorideCatalyst

Conditions

Temperature
50 °C

Procedure

A RBF was charged with perfluorophenyl 1-(4-bromo-5-fluoro-2-methylphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate (1.20 g, 2.075 mmol), (4-chloro-3-methylphenyl)boronic acid (1.061 g, 6.23 mmol), copper(i) chloride (0.616 g, 6.23 mmol), cesium carbonate (2.70 g, 8.30 mmol), and bis(di-tert-butyl(4-ethylaminophenyl)phosphine)-dichloropalladium(ii) (0.036 g, 0.05 mmol). The flask was flushed with Ar (g), then Dioxane (10.38 ml) was added. The reaction was heated to 50° C. and stirred for one hour. The reaction was diluted with ethyl acetate and washed three times with water containing excess n-(2-hydroxyethyl)ethylenediaminetriacetic acid, trisodium salt hydrate. The organic layer was washed with water, washed with brine, dried with sodium sulfate, filtered, and concentrated. The material was purified via column chromatography (RediSep Gold 120 g, gradient elution 0-30% EtOAc:Heptane) to afford perfluorophenyl 1-(4′-chloro-2-fluoro-3′,5-dimethyl-[1,1′-biphenyl]-4-yl)-2-oxo-1,2-dihydroquinoline-6-sulfonate (1.01 g, 1.619 mmol, 78% yield) as an off-white solid. m/z (ESI) 624.0 (M+H)+.

Workup

  1. customThe flask was flushed with Ar (g)
  2. additionDioxane (10.38 ml) was added
  3. additionThe reaction was diluted with ethyl acetate
  4. washwashed three times with water containing excess n-(2-hydroxyethyl)ethylenediaminetriacetic acid, trisodium salt hydrate
  5. washThe organic layer was washed with water
  6. washwashed with brine
  7. dry with materialdried with sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe material was purified via column chromatography (RediSep Gold 120 g, gradient elution 0-30% EtOAc:Heptane)

Sources & evidence

ORD record
ord-2b7c7644d0744dbdb8518e4c05f59434
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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