Method for preparing substituted triazolopyridines
A technology of alkyl and compound, which is applied in the field of intermediate compounds for the preparation of said compounds, and can solve the problems of undisclosed preparation of compounds, undisclosed, etc.
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Embodiment 0101
[0894] (2R)-2-(4-fluorophenyl)-N-[4-(2-{[2-methoxy-4-(methylsulfonyl)phenyl]amino}[1,2,4]tri Azolo[1,5-a]pyridin-6-yl)phenyl]propionamide
[0895]
[0896] Route 1
[0897] To a stirred suspension of Int08.011 (6.0 g) in DMF (48 mL) and dichloromethane (96 mL) was added sodium bicarbonate (3.69 g), (2R)-2-(4-fluorophenyl)propanoic acid ( 2.71 g) and HATU (8.36 g). The mixture was stirred at room temperature for 4 h. Water was added, and the mixture was stirred for 30 minutes. A half-saturated solution of sodium bicarbonate was added, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated sodium chloride solution, dried (sodium sulfate) and the solvent was removed in vacuo. Silica gel chromatography gave a solid which was triturated with ethyl acetate to afford 7.44 g of the title compound.
[0898] 1 H-NMR (400MHz, DMSO-d 6 ):δ[ppm]=1.40(d,3H),3.16(s,3H),3.84(q,1H),3.96(s,3H),7.09-7.18(m,2H),7.36-7.44(m, 3H),7.51(dd,1H),7.63-7...
Embodiment 0102
[0918] (2R)-N-[4-(2-{[2-Ethoxy-4-(methylsulfonyl)phenyl]amino}[1,2,4]triazolo[1,5-a]pyridine -6-yl)phenyl]-2-(4-fluorophenyl)propionamide
[0919]
[0920] 180 mg of the enantiomers of racemate 01.02.r were separated using chiral HPLC. Column: Chiralpak IA 5 μ 250x30; Flow rate: 20,0 mL / min; Solvent: A: Ethanol with 0.1% formic acid; Solvent: 100% A. Retention time of the title compound: 37.2-49.1 min (peak 2). Obtained: 74mg.
[0921] 1 H-NMR (300MHz, DMSO-d 6 ):δ[ppm]=1.35-1.49(m,6H),3.15(s,3H),3.84(q,1H),4.22(q,2H),7.07-7.19(m,2H),7.36-7.44( m,3H),7.50(dd,1H),7.61-7.78(m,5H),7.93(dd,1H),8.44-8.54(m,2H),9.10(d,1H),10.19(s,1H) .
[0922] [α] D 20 : -72.7° (in DMSO).
[0923] Column: Chiralpak IA 5 μl 50x4.6; Flow rate: 1,00 mL / min; Solvent: A: Ethanol with 0.1% formic acid; Solvent: 100% A. Running time: 30min. Retention time: 14.3min; UV254nm; Enantiomer ratio: 99%.
Embodiment 0103
[0925] (2R)-2-(4-fluorophenyl)-N-[4-(2-{[4-(methylsulfonyl)-2-(2,2,2-trifluoroethoxy)phenyl] Amino}[1,2,4]triazolo[1,5-a]pyridin-6-yl)phenyl]propionamide
[0926]
[0927] Route 1
[0928] To a stirred suspension of Int08.021 (5.6 g) in DMF (45 mL) and dichloromethane (90 mL) was added sodium bicarbonate (1.97 g), (2R)-2-(4-fluorophenyl)propanoic acid ( 2.17g) and HATU (6.69g). The mixture was stirred at room temperature for 4 h. Water was added, and the mixture was stirred for 30 minutes. A half-saturated solution of sodium bicarbonate was added, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated sodium chloride solution, dried (sodium sulfate) and the solvent was removed in vacuo. Chromatography of the amino phase on silica gel gave a solid which was triturated with a mixture of ethyl acetate and cyclohexane to afford 6.60 g of the title compound.
[0929] 1 H-NMR (300MHz, DMSO-d 6 ):δ[ppm]=1.39(d,3H),3.17(s,3H),3.83(q,1H...
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