Reaktion #710492

Reaktionsgleichung

ammonia

triflic anhydride

2-(3,5-dichloropyridin-2-yl)-2,2-difluoroethanol

pyridine

→

2-(3,5-dichloropyridin-2-yl)-2,2-difluoroethanamine

Lösungsmittel

brine

acetonitrile

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturwhile maintaining the temperature below 8° C
2. 2
   workup.ADDITIONwere added
3. 3
   Extraktionthe product extracted three times with 25 mL of ethyl acetate
4. 4
   SonstigeThe organic phases were collected
5. 5
   Waschenwashed three times with 40 mL of brine
6. 6
   Trocknendried over magnesium sulfate
7. 7
   SonstigeAfater evaporation of the solvent under vacuum 1.09 g of brown oil
8. 8
   Sonstigewere obtained
9. 9
   SonstigeAfter purification by column chromatography on silica gel (heptane/ethyl acetate gradient) 0.65 g (50%) of 2-(3,5-dichloropyridin-2-yl)-2,2-difluoroethanamine (IIa-15)
10. 10
    Sonstigewere obtained as a yellow oil, (M+1)=227, 19F-NMR (235 MHz, CDCl3) δ (ppm): −104.80 (CF2)

Vorschrift

To a solution of 1.3 g (5.7 mmol) of 2-(3,5-dichloropyridin-2-yl)-2,2-difluoroethanol (Int-9) in dry acetonitrile under argon, were added 0.744 mL (9.12 mmol) of dry pyridine. The reaction mixture was cooled to 0° C. and 1.06 mL (6.27 mmol) of triflic anhydride were added dropwise in 15 min while maintaining the temperature below 8° C. The reaction mixture was stirred at 0° C. for additional 30 min 9.9 mL of a 28% w/w aqueous solution of ammonia (144 mmol) were added and the reaction mixture was stirred at room temperature for 2 days. The reaction mixture was diluted with 50 mL of brine and the product extracted three times with 25 mL of ethyl acetate. The organic phases were collected, washed three times with 40 mL of brine and dried over magnesium sulfate. Afater evaporation of the solvent under vacuum 1.09 g of brown oil were obtained. After purification by column chromatography on silica gel (heptane/ethyl acetate gradient) 0.65 g (50%) of 2-(3,5-dichloropyridin-2-yl)-2,2-difluoroethanamine (IIa-15) were obtained as a yellow oil, (M+1)=227, 19F-NMR (235 MHz, CDCl3) δ (ppm): −104.80 (CF2).

Quelle