Sulfamic acid: as a green and reusable homogeneous catalyst for peroxidation of ketones and aldehydes using aqueous 30 % H2O2

Abstract

22, 23], (ii) reaction of ketals with H 2 O 2 in the presence of tungstic acid [24], or BF 3 ·Et 2 O [25], and (iv) peroxidation of ketones using an acidic solvent [26]. However, many of these methods have certain drawbacks including use of concentrated H 2 O 2 and excess acid, low yield, limited substrate range and production of mixtures of peroxidic products [27]. Also, poor selectivity and the presence of ozonesensitive groups in the substrates are further limitations in ozonolysis reaction. To avoid such limitations, recently, reactions of ketones and aldehydes with H 2 O 2 in the presence of Lewis acids in organic solvents have been reported. Among the Lewis acids, I 2 [28, 29], ceric ammonium nitrate (CAN) [30], CSA [31], NaHSO 4 ·SiO 2 [32], Re 2 O 7 [33], and PMA [34] have been reported as the catalysts in the synthesis of gem-dihydroperoxides with aqueous H 2 O 2 .In continuation of our efforts to explore new catalysts for synthesis of gem-dihydroperoxides [35,36]. Herein, we wish to introduce the sulfamic acid as a low-cost, green and effective recoverable solid catalyst in the synthesis of gemdihydroperoxides from ketones and aldehydes with 30 % aqueous H 2 O 2 at room temperature (Scheme 1).Sulfamic acid (SA) (NH 2 SO 3 H) is commercially available green heterogeneous catalyst that is solvable in water and has been used widely as an effective catalyst in organic synthesis [37,38]. ExperimentalSolvents, reagents, and chemical materials were obtained from Aldrich and Merck chemical companies and purified prior to use. Nuclear magnetic resonance spectra were recorded on JEOL FX 90Q using tetramethylsilane (TMS) as an internal standard. Infrared spectra were recorded on a PerkinElmer GX FT IR spectrometer (KBr pellets).Abstract Sulfamic acid has been used as an active, lowcost and reusable solid catalyst for conversion of ketones and aldehydes to corresponding gem-dihydroperoxides using 30 % aqueous hydrogen peroxide at room temperature. The reactions proceed with high rates and excellent yields.

Mild oxidative aromatization of 1,4-dihydropyridines with trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxalane promoted by ammonium bromide/HOAc in water/MeCN

“…Recently, gem-dihydroperoxides have been synthesized and have been used for oxidation reactions Bunge, Hamann, McCalmont, & Liebscher, 2009;Das, Krishnaiah, Veeranjaneyulu, & Ravikanth, 2007;Das, Veeranjaneyulu, Krishnaiah, & Balasubramanyam, 2008;Ghorai & Dussault, 2008;Li, Hao, Zhang, & Wu, 2009;Žmitek, Zupan, Stavber, & Iskra, 2006;Žmitek, Zupan, Stavber, & Iskra, 2007). We have synthesized trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxalane (Scheme 1) and used it as a powerful oxidant in some organic reactions (Azarifar & Khosravi, 2010a;Azarifar & Khosravi, 2010b;Azarifar, Khosravi, & Soleimanei, 2009;Azarifar, Najminejad, & Khosravi, 2013;Khosravi, 2014;Khosravi, 2015;Khosravi & Kazemi, 2012;Khosravi, Mobinikhaledi, Kazemi, Azarifar, & Rahmani, 2014;Khosravi, Pirbodaghi, Kazemi, & Asghari, 2015). So, in continuation of our interest in the application of DHPDMDOs, we used DHPDMDOs for in situ generation of Br + from NH 4 Br for catalysis of oxidative aromatization of 1,4-dihydropyridines to corresponding pyridines under mild conditions and short reaction times (Scheme 2).…”

Metal-Free and Efficient Epoxidation of α,β-Unsaturated Ketones with 1,1,2,2-Tetrahydroperoxy-1,2-Diphenylethane as a Powerful Solid Oxidant

“…Soon it was proven that these compounds have the potential to serve as oxidants, but their callous synthesis was an obstacle hindering their application as oxidants. In recent years, several methodologies have been elaborated for the easy preparation of gem ‐dihydroperoxides . Moreover, these compounds have important utility as oxidizing agents in a variety of procedures including epoxidation of α,β‐unsaturated ketones, as precursors for the synthesis of dicarboxylic acid esters, and as initiators for radical polymerization reactions, enantioselective oxidation of 2‐substituted 1,4‐naphtoquinones, and oxidation of sulfides and benzothiazoles .…”

“…As an extension of our interest in evaluating the oxidative potential of gem ‐dihydroperoxides, we were intrigued by the investigation through the synthesis (Scheme ) and application of 1,1,2,2‐tetrahydroperoxy‐1,2‐diphenylethane as a solid and efficient oxidant in the facile and metal‐free transformation of α,β‐unsaturated ketones to their corresponding epoxides under mild alkaline conditions at room temperature (Scheme ).…”

“…In recent years, several methodologies have been elaborated for the easy preparation of gem-dihydroperoxides. 24 Moreover, these compounds have important utility as oxidizing agents in a variety of procedures including epoxidation of α,β-unsaturated ketones, 25 as precursors for the synthesis of dicarboxylic acid esters, 26 and as initiators for radical polymerization reactions, 27 enantioselective oxidation of 2-substituted 1,4-naphtoquinones, 28 and oxidation of sulfides and benzothiazoles. 29 Also, they function as intermediates to yield numerous peroxides: for instance, tetraoxanes, 30,31 endoperoxides, 32 silateraoxanes, 33 spirobisperoxyketals, 34,35 bisperoxyketals, 36 and 1,2,4,5tetraoxacycloalkanes.…”

“…29 Also, they function as intermediates to yield numerous peroxides: for instance, tetraoxanes, 30,31 endoperoxides, 32 silateraoxanes, 33 spirobisperoxyketals, 34,35 bisperoxyketals, 36 and 1,2,4,5tetraoxacycloalkanes. 37,38 As an extension of our interest in evaluating the oxidative potential of gem-dihydroperoxides, 24,25,29,39 we were intrigued by the investigation through the synthesis (Scheme 1) 40 and application of 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane as a solid and efficient oxidant in the facile and metal-free transformation of α,β-unsaturated ketones to their corresponding epoxides under mild alkaline conditions at room temperature (Scheme 2).…”