Carbon Dioxide → (Diethylamino)sulfur trifluoride

Participants

Reaction Steps

a dry 1-l. four-necked round-bottomed flask is equipped with a thermometer (-100° to 50°), a solid carbon dioxide-cooled reflux condenser (protected from the atmosphere through a drying tube), a gas inlet tube above the liquid level, and a magnetic stirrer. The apparatus is flushed with dry nitrogen, and 300 ml of trichlorofluoromethane is added to the flask. As the nitrogen atmosphere is maintained, the trichlorofluoromethane is cooled to -70° by means of a solid carbon dioxide-acetone bath and 119 g (1.1 mole) of sulfur tetrafluoride is added from a cylinder through the gas inlet tube. The gas inlet tube is then replaced with a 250-ml pressure-equalized dropping funnel charged with a solution of 145 g (1 mole) of N,N-diethylaminotrimethylsilane in 90 ml trichlorofluoromethane. This solution is added dropwise, with stirring, to the sulfur tetrafluoride solution at a rate slow enough to keep the temperature of the reaction mixture below -60° (about 40 minutes). The cooling bath is removed, and the reaction mixture is allowed to warm spontaneously to room temperature. The condenser is replaced with a simple distillation head, and the solvent (bp 24°) and by-product fluorotrimethylsilane (bp 17°) are distilled off into a well cooled receiver by warming the reaction mixture gently to 45° by means of a heating mantle. The yellow to dark brown residual liquid is transferred and distilled at reduced pressure through a spinning band column to give 129-145 g (80-90%) of diethylaminosulfur trifluoride as a light yellow liquid, bp 46-47 (10 mm).

Provenance & Evidence