반응 #710492

반응 방정식

ammonia

triflic anhydride

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

pyridine

→

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

용매

brine

acetonitrile

반응 조건

후처리

1. 1
   온도while maintaining the temperature below 8° C
2. 2
   workup.ADDITIONwere added
3. 3
   추출the product extracted three times with 25 mL of ethyl acetate
4. 4
   기타The organic phases were collected
5. 5
   세척washed three times with 40 mL of brine
6. 6
   건조dried over magnesium sulfate
7. 7
   기타Afater evaporation of the solvent under vacuum 1.09 g of brown oil
8. 8
   기타were obtained
9. 9
   기타After 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
    기타were obtained as a yellow oil, (M+1)=227, 19F-NMR (235 MHz, CDCl3) δ (ppm): −104.80 (CF2)

실험 절차

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).

출처