Background and overview of the preparation method of (S)-(+)-m-nitrobenzene sulfonate glycidyl ester
(S)-(+)-m-nitrobenzene sulfonate glycidyl ester is an organic intermediate, which can be synthesized from 3-nitrobenzene sulfonyl chloride and s-glycidol or (R)-3-chloro-1 , obtained by the reaction of 2-propanediol.
Preparation method of (S)-(+)-m-nitrobenzene sulfonate glycidyl ester
Preparation method report 1 of (S)-(+)-m-nitrobenzene sulfonate glycidyl ester,
To a stirred solution of s-glycidol (CAS No. 556-52-5, available from Sigma-India) (1.67g, 22.560mmol) in dichloromethane (50ml) at 0°C was added triethyl Amine (3.90 ml, 27.070 mmol) 15 min. 3-nitrobenzenesulfonyl chloride (CAS No. 121-51-7, available from combi-blocks) (5.00 g, 22.560 mmol) was added to the above reaction mixture, and the reaction mixture was stirred at the same temperature for 1 hour. The resulting reaction mixture methoxypyridine was poured into water (200 ml) and extracted with dichloromethane (2 x 100 ml). The combined organic phases were dried over Na2SO4, filtered and concentrated under reduced pressure. The resulting crude material was triturated using n-pentane to obtain ethylene oxide-2-ylmethyl 3-nitrobenzene sulfonate ethyl ester (5.00 g, 19.305 mmol).
Preparation method report 2 of (S)-(+)-m-nitrobenzene sulfonate glycidyl ester,
Add 499 g of tripotassium phosphate to 1.2 liters of (R)-3-chloro-1,2-propanediol (200 g, optical purity 99.5% ee) in methylene chloride, and then stir the resulting solution Reflux for 3 hours. The resulting solution was cooled to 0°C, and 201 g of triethylamine, 4 g of 4-(dimethyl)pyridine and 401 g of 3-nitrobenzenesulfonyl chloride were added to the solution. After stirring for an additional hour at room temperature, the reaction mixture was washed successively with 2.2 liters of 5% aqueous potassium carbonate solution, 2 liters of indium aqueous hydrogen chloride solution and 1 liter of water. The organic layer was dried over 50 g of anhydrous sodium sulfate and filtered. Dichloromethane was evaporated under reduced pressure to give the crude product (chemical purity: 99.3%, optical purity (GC) 99.54%ee). Yield: 378g, 80.5%; chemical purity: 99.2%; optical purity (GC): 99.5%ee; melting point: 64~66°C.
References
[1] [Invented in China] CN201880032332.4 Compounds for treating or preventing PRMT5-mediated diseases
[2] [Chinese invention, Chinese invention authorization] CN200480044254.8 A method for preparing glycidyl magnesium carbonate derivatives
