反応 #352494

反応方程式

diethylazodicarboxylate

2-(trifluoromethyl)phenol

3-(hydroxymethyl)-6-[(tert-butyldimethylsilyloxy)methyl]-1,2-dithiin

triphenylphosphine

→

3-[(tert-butyldimethylsilyloxy)methyl]-6-[(2-trifluoromethylphenyloxy)methyl]-1,2-dithiin

収率 37.0%

溶媒

ethyl acetate hexane

THF

THF

反応条件

後処理

1. 1
   その他was kept at 0°-5° C. until TLC analysis
2. 2
   その他the reaction
3. 3
   workup.ADDITIONFor isolation of the products, the reaction mixture poured directly onto a silica gel column

実験手順

To a stirred solution of 3-(hydroxymethyl)-6-[(tert-butyldimethylsilyloxy)methyl]-1,2-dithiin (U.S. Ser. No. 08/212,096) (200 mg, 0.69 mmol) in 5 mL dry THF was added a solution of 2-(trifluoromethyl)phenol (223 mg, 1.37 mmol) in 5 mL THF, followed by addition of triphenylphosphine (234 mg, 0.89 mmol) The resulting solution was cooled to 0° C., then 140 μL (156 mg, 0.89 mmol) of diethylazodicarboxylate was added, and the reaction mixture was kept at 0°-5° C. until TLC analysis showed the reaction to be complete. For isolation of the products, the reaction mixture poured directly onto a silica gel column using ethyl acetate-hexane, 1:3, to provide 110 mg (37%) of 3-[(tert-butyldimethylsilyloxy)methyl]-6-[(2-trifluoromethylphenyloxy)methyl]-1,2-dithiin; 1H NMR (CDCl3):δ7.56 (d, J=8.0, 1 H), 7.45 (t, J=8.0, 1 H), 7.01 (m, 2 H), 6.49 S (d, J=6.0 Hz, 1 H), 6.37 (d, J=6.0 Hz, 1 H), 4.71 (s, 2 H), 4.26 (s, 2 H), 0.88 (s, 9 H), 0.07 (s, 6 H); 13C NMR (CDCl3):δquaternary carbons missing, 136.19, 133.24, 127.23, 123.57, 120.81, 113.15, 69.58, 64.85, 25.79, 18.34, -5.38; MS (LSIMS) (M+) 434.1.

出典