Novel hydroperoxy sultam, 2-(6-bromo-pyrid-2-yl)-2,3,4,5,6,7-hexahydro-1,2-benzisothiazol-3-hydroperoxy 1,1-dioxide: synthesis, crystal structure and kinetics of catalytic interaction with cyclooctene

Abstract

The novel hydroperoxy sultam, 2-(6-bromo-pyrid-2-yl)-2,3,4,5,6,7-hexahydro-1,2-benzisothiazol-3hydroperoxy 1,1-dioxide (HPS), was synthesized by the oxidation of the isothiazolium salt with hydrogen peroxide. As established by X-ray crystallography the unit cell of HPS in crystal state includes four molecules with a dimeric structure as a result of strong intermolecular hydrogen bond formation. The hydroperoxy sultam interacts with cyclooctene in the presence of molybdenum boride MoB as epoxidation catalyst at 40 1C. The additional consumption of HPS upon catalyst activation leads to an increase in the 1,2-epoxycyclooctane formation selectivity with increasing of HPS concentration. On the basis of the obtained results a kinetic reaction scheme was proposed. The equation for the reaction rate as well as the equation that connects the current concentration of hydroperoxide with reaction time and allows the calculation of the theoretical kinetic curves for HPS consumption were derived according to the kinetic scheme.

Electron-Deficient Heteroarenium Salts: An Organocatalytic Tool for Activation of Hydrogen Peroxide in Oxidations

“…The reactivity of the hydroperoxy function is significantly enhanced by its connection to an electron-deficient heterocyclic ring, which was demonstrated in metal-free oxidations with several heterocyclic hydroperoxides of various structures; however, most of these compounds are used as stoichiometric oxidants prepared in advance. , The use of reactive hydroperoxides generated in a catalytic cycle remains the domain of organocatalytic oxidations mediated by flavinium salts 1 or 2 (Scheme and ). , As shown in Scheme in the example of isoalloxazinium derivative 1 , flavinium catalysts react with hydrogen peroxide to form flavin-4a-hydroperoxide 1-OOH . After oxygen is transferred to a substrate, the catalyst is regenerated by water elimination from a pseudobase 1-OH .…”

Recent Developments in the Synthesis of Fused Sultams

“…Recently, the hydroperoxy bicyclic sultam 2-(6-bromo-pyrid-2-yl)-2,3,4,5,6,7-hexahydro-3-hydroperoxy-1,2-benzisothiazol-1,1-dioxide (HPS) was prepared as a reagent for the catalyzed selective epoxidation of cyclooctene. HPS 27.4 was obtained by oxidation of the isothiazolium salt 27.3 with 30% H 2 O 2 in glacial acetic acid at room temperature (Scheme ).…”

Synergistic Effect of BaCl2 on Corrosion Inhibition of Copper by Mentha Spicata Oil in 1M Nitric Acid: Gravimetric and Raman Spectroscopy Studies

“…[26][27][28][29][30][31] Among them, molybdenum compounds show much promise due to high catalytic activity. [32][33][34][35] In particular, molybdenum boride catalysts are quite effective in the epoxidation reactions of olefins with tert-butyl hydroperoxide. [36][37][38][39][40][41] By using these catalysts, the rate of hydroperoxide consumption flow rate increases over time.…”