1种三氟甲基磺酰氟合成新方法

A New Method for the Synthesis of Trifluoromethyl Sulfonyl Fluoride

研究采用连二亚硫酸钠和三氟溴甲烷反应生成三氟甲基亚磺酸钠,然后用氯气直接氧化得到三氟甲基磺酰氯,再用无水氟化氢氟化的方法制备三氟甲基磺酰氟。结果表明,亚磺化反应180 mL H_(2)O、25 g Na_(2)CO_(3),溶解后加入40 g Na_(2)S_(2)O_(4),溶解后加入60 mL C_(2)H_(5)OH、30 g CF_(3)Br,加热到30℃左右,反应数小时,得到三氟甲基亚磺酸钠,收率70%。氯化反应,50 g三氟甲基亚磺酸钠粗品,80 mL H_(2)O,机械搅拌,冰浴,缓慢通入氯气,得到三氟甲基磺酰氯,收率80%以上。氟化反应,氯化产物经真空干燥箱在40℃下干燥后,以HF为氟化剂,SbCl_(5)为催化剂进行氟化反应,收率99.5%。该方法具有原料易得,方法简单,便于控制。

Sodium trifluoromethylsulfinate was prepared by the reaction of sodium dithionite and trifluorobromomethane,and then trifluoromethylsulfonyl chloride was obtained by direct oxidation with chlorine gas,and then trifluoromethylsulfonyl fluoride was prepared by anhydrous hydrogen fluoride fluorination.The results showed that sodium trifluoromethylsulfinate was obtained by sulfitation reaction of 180 mL H_(2)O,25 g Na_(2)CO_(3),adding 40 g Na_(2)S_(2)O_(4) after dissolution,adding 60 mL C_(2)H_(5)OH,30 g CF_(3)Br after dissolution,heating to about 30℃ for several hours.The yield was 70%.Chlorination reaction,50 g sodium trifluoromethylsulfinate crude,80 mL H_(2)O,mechanical stirring,ice bath,slowly into the chlorine gas to obtain trifluoromethylsulfonyl chloride,the yield of more than 80%.The chlorination product was dried by vacuum drying oven at 40℃,and then fluorination reaction was carried out with HF as fluorination agent and SbCl_(5) as catalyst.The yield was 99.5%.The method has the advantages of easy availability of raw materials,simple method and convenient control.