反応 #414342

反応方程式

water

thionyl chloride

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

(4-Amino-2-cyanophenyl)phenyl sulfide

→

N-(4-phenylthio-3-cyanophenyl)-3,3,3,-trifluoro-2-hydroxy-2-methylpropanamide

収率 158.7%

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 two 100 mL portions of ethyl ether
4. 4
   その他The oil obtained-on removal of the ethyl ether
5. 5
   その他was chromatographed on 325 g of silica gel using an ethyl ether (0%, 5%, 10% and 20%) in methylene chloride gradient
6. 6
   その他the solvent removed in vacuo

実験手順

To a stirred, cooled (-20° C.) solution of 3,3,3-trifluoro-2-hydroxy-2-methylpropanoic acid (2.16 g 13.7 mmol) in N,N-dimethylacetamide (20 mL) was rapidly added thionyl chloride (1.73 g, 14.5 mmol) and the mixture (a precipitate formed after a few minutes) stirred at -20° C. to -10° C. for 1 hour. (4-Amino-2-cyanophenyl)phenyl sulfide (2.08 g, 9.2 mmol) was then added in one portion and the mixture allowed to stir at room temperature overnight. The solution was poured into 500 mL of water and extracted with two 100 mL portions of ethyl ether. The oil obtained-on removal of the ethyl ether was chromatographed on 325 g of silica gel using an ethyl ether (0%, 5%, 10% and 20%) in methylene chloride gradient. The proper fractions were combined, the solvent removed in vacuo and the residue heated overnight at 60° C./0.1 mm to yield 5.35 g (93%) of N-(4-phenylthio-3-cyanophenyl)-3,3,3,-trifluoro-2-hydroxy-2-methylpropanamide, mp 124°-126° C. 1H--NMR (300 MHz, d6 --DMSO): 1.59 (s, 3H, CH3), 7.32-7.47 (m, 6H, aromatic), 7.59 (s, 1H, OH), 8.07 (dd 1H, J=8.8, 2.3 Hz, aromatic), 8.33 (d, 1H, J=2.3 Hz, aromatic), 10.48 (s, 1H, NH). MS (CI, CH4): 367(M+1).

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