2,3-Bis(phenylsulfonyl)-1,3-butadiene

Abstract

[85540-20-1] C16H14O4S2 (MW 334.41) InChI = 1S/C16H14O4S2/c1-13(21(17,18)15-9-5-3-6-10-15)14(2)22(19,20)16-11-7-4-8-12-16/h3-12H,1-2H2 InChIKey = MZRCSZMGBMHTJW-UHFFFAOYSA-N (electrophilic 4-carbon annulation reagent; electron-deficient diene component; sulfonyl allene precursor) Alternate Name: bPSB. Physical Data: white crystalline solid, mp 181–183 °C. Solubility: soluble in CH2Cl2, THF, o-DCB, acetonitrile, and toluene. Preparative Methods: the title reagent can be prepared by the reaction of 2-butyne-1,4-diol with phenylsulfenyl chloride, followed by oxidation of the resulting bis(sulfoxide) with hydrogen peroxide, according to the following procedure. A solution of 2-butyne-1,4-diol (90 mmol) and triethylamine (270 mmol) in dichloromethane (700 mL) is treated with phenylsulfenyl chloride (180 mmol) over 0.5 h at −78 °C. After warming to room temperature and stirring for 12 h, the reaction mixture is subjected to aqueous extraction, dried, and concentrated to give a residue which is recrystallized (MeOH/Et2O) to provide the bis(sulfoxide) in 74% isolated yield. A solution of this compound (56.3 mmol) and 33% hydrogen peroxide (366 mmol) in glacial acetic acid (170 mL) is subsequently heated to 90 °C for 5 h, after which the reaction mixture is diluted with water and allowed to cool to room temperature. The resulting white precipitate is collected by filtration, dried, and recrystallized (CH2Cl2/hexane) to give the title compound in 61% yield.1, 2 Purification: recrystallization from CH2Cl2/hexane (1:1). Handling, Storage, and Precautions: neither air-nor moisture-sensitive; should be stored in a tightly closed bottle under nitrogen, shelf-stable for several years. Toxicity has not been determined.