反応 #414352

反応方程式

water

thionyl chloride

3,3,3-trifluoro-2-hydroxy-2-methylpropanoic acid

4-Cyano-3-phenylthiobenzenamine

→

propanamide

収率 94.8%

N-(4-Cyano-3-phenylthiophenyl)-3,3,3,-trifluoro-2-hydroxy-2-methyl propanamide

収率 94.8%

溶媒

N,N-dimethylacetamide

反応条件

後処理

1. 1
   その他the mixture (a precipitate formed after a few minutes)
2. 2
   workup.STIRRINGto stir at room temperature overnight
3. 3
   抽出extracted with ethyl ether (2×100 mL)
4. 4
   乾燥the etheral extracts dried (MgSO4)
5. 5
   ろ過filtered
6. 6
   その他the solvent removed in vacuo
7. 7
   その他The residue was chromatographed on 315 g of silica gel using a ethyl ether (0%, 10%, and 20%) in methylene chloride gradient
8. 8
   その他the solvent removed in vacuo
9. 9
   workup.DISSOLUTIONthe residue dissolved in a mixture of 100 mL hexane and 150 mL methylene chloride
10. 10
    workup.DISTILLATIONMost of the methylene chloride was distilled off as the solution
11. 11
    温度After cooling the solid
12. 12
    その他was collected
13. 13
    その他dried at 85° C. /0.1 mm

実験手順

To a stirred, cooled (-20° C.) solution of 3,3,3-trifluoro-2-hydroxy-2-methylpropanoic acid (1.62 g 10.2 mmol) in N,N-dimethylacetamide (15 mL) was rapidly added thionyl chloride (1.30 g, 10.9 mmol) and the mixture (a precipitate formed after a few minutes) stirred at -20° C. to -5° C. for 1 hour. 4-Cyano-3-phenylthiobenzenamine (1.55 g, 6.85 mmol) was then added in one portion and the mixture allowed to stir at room temperature overnight. The solution was poured into water, extracted with ethyl ether (2×100 mL); the etheral extracts dried (MgSO4), filtered and the solvent removed in vacuo. The residue was chromatographed on 315 g of silica gel using a ethyl ether (0%, 10%, and 20%) in methylene chloride gradient. The proper fractions were combined, the solvent removed in vacuo and the residue dissolved in a mixture of 100 mL hexane and 150 mL methylene chloride. Most of the methylene chloride was distilled off as the solution was scratched to induce crystal growth. After cooling the solid was collected and dried at 85° C. /0.1 mm to yield the title propanamide (2.38 g, 91%); mp 111°-113° C. 1H--NMR (250 MHz, CDCl3): 1.67 (s, 3H, CH 3), 3.68 (s, 1H, OH), 7.27 (d, 1H, J=1.9 Hz, aromatic), 7.40-7.51 (m, 5H, aromatic), 7.59-7.69 (m, 2H, aromatic), 8.51 (s, 1H, NH). MS (CI, CH4): 367(M+1).

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