Bis(phenylsulfonyl)sulfur Diimide

Abstract

[667-20-9] C12H10N2O4S3 (MW 342.40) 1S/C12H10N2O4S3/c15-20(16,11-7-3-1-4-8-11)13-19-14-21(17,18)12-9-5-2-6-10-12/h1-10H InChIKey = WDFKHANKUMDDBM-UHFFFAOYSA-N (electrophilic source of nitrogen; electron-deficient dienophile) Physical Data: yellow crystalline solid, mp 109–110 °C. 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.0 Hz, 2H), 7.67 (t, J = 8.0 Hz, 1H), 7.53 (t, J = 8.0 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 137.9, 135.0, 129.6, 128.3. IR (thin film): 3348, 3255, 1557, 1332, 1159 cm−1. Form Supplied in: commercially available as a yellow solid. Solubility: soluble in CH2Cl2, 1,2-dimethoxyethane, ethyl acetate, THF, and Et2O. Preparative Methods: the title reagent can be prepared by the reaction of benzenesulfonamide and thionyl chloride followed by treatment with pyridine, according to the following procedure. A solution of benzenesulfonamide (50 g, 0.318 mol) and thionyl chloride (80 mL, 1.1 mol) in benzene (30 mL) is refluxed at 80 °C for 3 days (over the course of the reaction, the mixture becomes a clear solution). When the starting material is consumed by 1H NMR analysis of an aliquot, the mixture is concentrated under vacuum to remove benzene and excess SOCl2. Trace amounts of SOCl2 are removed by redissolving the residue in toluene (50 mL), concentrating under reduced pressure, and storing under vacuum at 50 °C for 6 h. The residue is then treated with benzene (70 mL) and slightly heated to ensure all materials dissolve in the solvent. Once the solution is cooled to 23 °C, pyridine (0.5 mL) is added, and the mixture is stirred. After 12 h, stirring is ceased, and a yellow precipitate slowly crystallizes from the solution. The precipitate is separated by vacuum filtration and stored under vacuum at 50 °C for 8 h. The resulting yellow solid is collected to give the title compound in 98% yield.1, 2 Purification: recrystallization from benzene. Handling, Storage, and Precaution: since the title compound is sensitive to water, it should be stored in a dessicator inside a sealed flask that has been purged with N2. Toxicity has not been determined.