The reactor is a three-necked flask with a volume of 250 ml, equipped with a thermometer, mechanical stirring, a reflux condenser and a drying tube. 18.9 g of Para Toluenesulfonyl Chloride (100 mmol), 0.73 g of N,N-dimethylformamide (10 mmol) and 50 g of dichloroethane were added in one portion to the flask. Start stirring, at room temperature, the dichloroethane solution (which contains 10g triphosgene (34mmol), 50g dichloroethane) dissolved with triphosgene is slowly and uniformly added dropwise to the reaction flask, and the time for adding is 30min. Incubate for 30min after adding. After the heat preservation, the temperature was raised to an obvious reflux phenomenon in the system, and the reaction was maintained under reflux conditions for three hours. After the reaction solution was cooled, the filter cake ammonium chloride was removed by filtration, and the obtained filtrate was subjected to vacuum distillation. After 92 g of methylene chloride was recovered, the remaining filtrate was placed in a cold storage with a temperature of -10 ℃ – 0 ℃ for 24 hours, 16.5 g of white needle-like crystals were obtained, and the purity of Para Toluenesulfonyl Chloride was 98.5% by chromatographic analysis, and the yield was 85.31%.
In a 250mL reaction flask equipped with a constant pressure funnel, a stirrer and a condenser, add 30g (0.082mol, 1.0eq) of magnesium p-toluenesulfonate, add 30mL of N,N-diformylformamide solvent, and stir to make p-toluene Magnesium sulfonate was uniformly suspended in N,N-diformylformamide, 10.7g SOCl2 (0.090mol, 1.1eq) was added dropwise under argon protection, the dropping was completed, the temperature was raised to 75°C, and the reaction was maintained until the system was dissolved ( About 2 to 4 hours); add 60 mL of toluene dropwise to the system, keep stirring for 30 minutes, then cool to room temperature, add 60 mL of water, stir and separate the liquid, wash the collected organic layer with saturated saline, anhydrous sodium sulfate Dry and concentrate under reduced pressure to obtain 30.1 g of solid Para Toluenesulfonyl Chloride (purity 99.7%, molar yield 96%).
Dissolve 0.1mol (19.02g) p-toluenesulfonic acid (with crystal water, the same below) and 0.38g [BuPy]EtOSO3 in 47.55g chloroform, stir evenly, and add 0.15mol (17.48g) chlorine dropwise at 25°C Sulfonic acid. After 2.5 hours of constant temperature reaction, 0.1 mol (1.8 g) of distilled water was added to remove excess chlorosulfonic acid. The reaction solution was layered, and the waste acid and the organic phase were obtained by separating liquids through a separatory funnel. The organic phase was washed with 10 g of distilled water, and the residual p-toluenesulfonic acid in the organic phase was removed. The partition coefficient of p-toluenesulfonic acid is the ratio of the concentration of p-toluenesulfonic acid in the organic phase to the concentration in the spent acid. Analysis by liquid chromatography showed that the partition coefficient of p-toluenesulfonic acid was 0.0494; chloroform was recovered by distilling the organic phase to obtain 16.67 g of Para Toluenesulfonyl Chloride with a yield of 87.51%.
At room temperature, add 100 g of crude sodium p-toluenesulfonate salt, 200 ml of toluene, 1 ml of N,N-dimethylformamide and 67 g of thionyl chloride to a round-bottomed flask (500 mL), mix and stir for 5 minutes Then, the temperature was raised to 65°C and reacted for 8 hours, the reaction was changed to a vacuum distillation device, toluene was evaporated from the reaction solution, and after evaporation to dryness, the temperature was lowered to room temperature, 40 ml of cyclohexane was added, and the product was obtained by filtration after heating and cooling. 93 g, 95% yield.
In a 2000-liter reactor, a stirrer, a dropping funnel, a thermometer, a gas exporter, and a water absorption device for exporting the gas were installed, and 7.5 moles of chlorosulfonic acid were firstly added to the flask, and heated to about 50 °C under stirring. 2 moles of ammonium chloride were added in portions, then the temperature of the reaction content was raised to 79-86 °C, 5 moles of toluene was added dropwise, after dropping, the temperature was lowered to 35-40 °C, the other half of chlorosulfonic acid was added, and the reaction was continued for 1 After 2 hours, the temperature of the contents was lowered to 20-25°C and placed for 2 hours. At this time, almost all the para-chlorine crystals were precipitated. The crystals were separated by filtration, washed with water, and then the ortho-isomer was separated to obtain the final product pair. Para Toluenesulfonyl Chloride , the content is more than 95%, the water content is about 4.0%, the melting point is about 65°C, the yield (calculated in toluene) is 78%, and the total yield including the ortho-isomer is 86-87%.