Reacción #1591649

Ecuación de reacción

6-(benzylthio)-1-(4-bromo-2-methoxy-5-methylphenyl)quinolin-2(1H)-one

water

water

1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione

2,3,4,5,6-pentafluorophenol

triethylamine

→

perfluorophenyl 1-(4-bromo-2-methoxy-5-methylphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate

Rendimiento 62.9%

Disolventes

acetic acid

DCM

Condiciones de reacción

Tratamiento posterior

1. 1
   Otroto give clear
2. 2
   TemperaturaThe flask was cooled in an ice-water bath for 10 min
3. 3
   workup.ADDITIONan additional portion of oxidant (850 mg) was added
4. 4
   workup.ADDITIONwere added in sequence
5. 5
   workup.WAITAfter 20 min
6. 6
   OtroThe layers were separated
7. 7
   Extracciónthe aq. layer was extracted with DCM (1×)
8. 8
   SecadoThe combined organic extracts were dried over sodium sulfate
9. 9
   Filtraciónfiltered
10. 10
    Concentraciónconcentrated
11. 11
    OtroThe residue was purified by chromatography on silica gel (80-g Redi-Sep Gold column, 25-g silica gel loading column, 10-60% EtOAc/Heptane with 10% DCM)
12. 12
    workup.ADDITIONFractions containing the main spot
13. 13
    Concentraciónconcentrated
14. 14
    Otroto give an off-white foam

Procedimiento

A RBF was charged with 6-(benzylthio)-1-(4-bromo-2-methoxy-5-methylphenyl)quinolin-2(1H)-one (4.23 g, 9.07 mmol), DCM (71.1 ml), acetic acid (2.67 ml), and water (1.778 ml) to give clear, light-brown. The flask was cooled in an ice-water bath for 10 min, then 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (3.66 g, 18.59 mmol) was added in one portion. After 40 min, an additional portion of oxidant (850 mg) was added. The mixture was stirred for another 20 min, then 2,3,4,5,6-pentafluorophenol (2.504 g, 13.60 mmol) and triethylamine (5.06 ml, 36.3 mmol) (added dropwise) were added in sequence. After 20 min, the mixture was diluted with water. The layers were separated, and the aq. layer was extracted with DCM (1×). The combined organic extracts were dried over sodium sulfate, filtered, and concentrated. The residue was purified by chromatography on silica gel (80-g Redi-Sep Gold column, 25-g silica gel loading column, 10-60% EtOAc/Heptane with 10% DCM). Fractions containing the main spot were combined and concentrated to give an off-white foam. LCMS and NMR showed that it was contaminated with 30 mol % of the peak with a mass of 425. This was equal to 82 wt % purity. This meant a yield of product: perfluorophenyl 1-(4-bromo-2-methoxy-5-methylphenyl)-2-oxo-1,2-dihydroquinoline-6-sulfonate (3.37 g, 5.71 mmol, 62.9% yield). m/z (ESI) 590.0 (M+H)+.

Fuente