10297-73-1Relevant articles and documents
[γ-1,2-H2SiV2W10O40] immobilized on surface-modified SiO2 as a heterogeneous catalyst for liquid-phase oxidation with H2O2
Kasai, Jun,Nakagawa, Yoshinao,Uchida, Sayaka,Yamaguchi, Kazuya,Mizuno, Noritaka
, p. 4176 - 4184 (2006)
An organic-inorganic hybrid support has been synthesized by covalently anchoring an N-octyldihydroimidazolium cation fragment onto SiO2 (denoted as 1-SiO2). This modified support was characterized by solid-state 13C, 29Si, and 31P NMR spectroscopy, IR spectroscopy, and elemental analysis. The results showed that the structure of the dihydroimidazolium skeleton is preserved on the surface of SiO2. The modified support can act as a good anion exchanger, which allows the catalytically active polyoxometalate anion [γ-1,2-H 2SiV2W10O40]4- (I) to be immobilized onto the support by a stoichiometric anion exchange (denoted as I/1-SiO2). The structure of anion I is preserved after the anion exchange, as confirmed by IR and 51V NMR spectroscopy. The catalytic performance for the oxidation of olefins and sulfides, with hydrogen peroxide (only one equivalent with respect to substrate) as the sole oxidant, was investigated with I/1-SiO2. This supported catalyst shows a high stereospecificity, diastereoselectivity, regioselectivity, and a high efficiency of hydrogen peroxide utilization for the oxidation of various olefins and sulfides without any loss of the intrinsic catalytic nature of the corresponding homogeneous analogue of I (i.e., the tetra-n-butylammonium salt of I, TBA-I), although the rates decreased to about half that with TBA-I. The oxidation can be stopped immediately by removal of the solid catalyst, and vanadium and tungsten species' can hardly be found in the filtrate after removal of the catalyst. These results rule out any contribution to the observed catalysis from vanadium and tungsten species that leach into the reaction solution, which means that the observed catalysis is truly heterogeneous in nature. In addition, the catalyst is reusable for both epoxidation and sulfoxidation without any loss of catalytic performance.
Electronic and steric effects on the oxygenation of organic sulfides and sulfoxides with oxo(salen)chromium(V) complexes
Venkataramanan, Natarajan Sathiyamoorthy,Premsingh, Sundarsingh,Rajagopal, Seenivasan,Pitchumani, Kasi
, p. 7460 - 7470 (2003)
The kinetics of oxygenation of several para-substituted phenyl methyl sulfides and sulfoxides with a series of 5-substituted and sterically hindered oxo(salen)chromium(V) complexes have been studied by a spectrophotometric technique. Though the reaction of sulfides follows simple second-order kinetics, sulfoxides bind strongly with the metal center of the oxidant and the oxygen atom is transferred from the oxidant-sulfoxide adduct to the substrate. The reduction potentials, Ered, of eight Cr(V) complexes correlate well with the Hammett a constants, and the reactivity of the metal complexes is in accordance with the Ered values. The metal complexes carrying bulky tert-butyl groups entail steric effects. Organic sulfides follow a simple electrophilic oxidation mechanism, and the nonligated sulfoxides undergo electrophilic oxidation to sulfones using the oxidant-sulfoxide adduct as the oxidant. Sulfoxides catalyze the Cr(V)-salen complexes' oxygenation of organic sulfides, and the catalytic activity of sulfoxides is comparable to pyridine N-oxide and triphenylphosphine oxide. The rate constants obtained for the oxidation of sulfides and sulfoxides clearly indicate the operation of a pronounced electronic and steric effect in the oxygenation reaction with oxo(salen)chromium(V) complexes.
Mechanism of oxygenation of aryl methyl and diaryl sulphoxides by peroxomonophosphoric acid
Suthakaran,Rajagopal,Srinivasan
, p. 1369 - 1374 (2001)
The kinetics of oxygenation of the title sulphoxides by peroxomonophosphoric acid in aqueous acetic acid follows an overall second-order kinetics, first-order in each reactant. An analysis of the influence of [H+] reveals that H3PO5 is the active species in the oxidation. The structure - reactivity studies with different substituents on the phenyl ring give evidence for the formation of an electron deficient sulphonium ion intermediate as the correlation between log k2 and σ gives a negative ρ value (ρ=-0.47±0.09, r=0.988, s=0.03 at 35°C for aryl methyl sulphoxides and ρ=-0.54±0.11, r=0.983, s=0.07 at 35°C for diaryl sulphoxides). It is proposed that the mechanism involves the nucleophilic attack of the sulphoxide sulphur on the peroxo-oxygen of H3PO5 in the rate-limiting step.
Design, synthesis, and biological evaluation of new pyrazino[1,2-a]benzimidazole derivatives as selective cyclooxygenase (COX-2) inhibitors
Azami Movahed, Mahsa,Daraei, Bahram,Shahosseini, Soraya,Esfahanizadeh, Marjan,Zarghi, Afshin
, (2019)
A new class of pyrazino[1,2-a]benzimidazole derivatives possessing the SO2Me pharmacophore at the para position of the C-3 phenyl ring was designed, synthesized, and tested for their cyclooxygenase-2 (COX-2) inhibitory, anti-cancer and anti-platelet aggregation activities. In vitro COX-1/COX-2 inhibition studies showed that 2-(4-methylphenyl)-1-methylene-3-(4-(methylsulfonyl)phenyl)-1,2-dihydropyrazino-[1,2-a]benzimidazole (5g) was the most potent COX-2 inhibitor (IC50 = 0.08 μM) and 2-(3,4,5-trimethoxyphenyl)-1-methylene-3-(4-(methylsulfonyl)phenyl)-1,2-dihydropyrazino-[1,2-a]benzimidazole (5m) had the highest selectivity index (SI > 909). Cytotoxicity of the synthesized compounds was also determined against the MCF-7 cell line. Most compounds were cytotoxic against MCF-7 cells and our results showed that compound 5m exhibited the highest anti-proliferative activity compared to the reference compound, cisplatin. Our data also indicated that compound 5k was the most potent platelet aggregation inhibitor according to aggregometry test results.
Copper-catalyzed aerobic oxidation and cleavage/formation of C-S bond: A novel synthesis of aryl methyl sulfones from aryl halides and DMSO
Yuan, Gaoqing,Zheng, Junhua,Gao, Xiaofang,Li, Xianwei,Huang, Liangbin,Chen, Huoji,Jiang, Huanfeng
, p. 7513 - 7515 (2012)
With atmospheric oxygen as the oxidant, a novel copper(i)-catalyzed synthesis of aryl methyl sulfones from aryl halides and widely available DMSO is described. The procedure tolerates aryl halides with various functional groups (such as methoxy, acetyl, chloro, fluoro and nitro groups), which could afford aryl methyl sulfones in moderate to high yields. The copper-catalyzed aerobic oxidation and the cleavage/formation of C-S bond are the key steps for this transformation.
Tantalum carbide or niobium carbide catalyzed oxidation of sulfides with hydrogen peroxide: Highly efficient and chemoselective syntheses of sulfoxides and sulfones
Kirihara, Masayuki,Itou, Atsushi,Noguchi, Takuya,Yamamoto, Junya
, p. 1557 - 1561 (2010)
The oxidation of sulfides with 30% hydrogen peroxide catalyzed by tantalum carbide provided the corresponding sulfoxides in high yields. The reaction of sulfides with 30% hydrogen peroxide catalyzed by niobium carbide efficiently afforded the corresponding sulfones. These catalysts can easily be recovered from the reaction mixture and may be repeatedly used as catalysts for the oxidation without losing their activity. Georg Thieme Verlag Stuttgart New York.
Efficient and convenient oxidation of sulfides to sulfones using H 2O2 catalyzed by V2O5 in ionic liquid [C12mim][HSO4]
Hu, Yu-Lin,Liu, Xiao-Bing,Fang, Dong
, p. 38 - 42 (2014)
A simple, efficient, and eco-friendly procedure for the oxidation of sulfides to sulfones using H2O2 catalyzed by V 2O5 in ionic liquid [C12mim][HSO4] has been developed. This atom-economical protocol affords the target products in good to high yields. The products can be separated by a simple extraction with organic solvent, and the catalytic system can be recycled and reused without loss of catalytic activity.
Design, synthesis and biological evaluation of new imidazo[1,2-a]pyridine derivatives as selective COX-2 inhibitors
Abdel-Rahman, Hamdy M.,Ali, Mohammed R. A.,Amin, Noha H.,Elsaadi, Mohammed T.,Ismael, Ahmed S.
, (2021/10/22)
Three new series of methylsulfonyl-containing imidazo[1,2-a]pyridines 8a-d, 9a-d and 10a-d were designed and synthesized. Characterization of the chemical structure of these new compounds was performed using spectral and elemental analyses. The synthesized derivatives were tested for their ability to inhibit COX-1 and COX-2 isozymes in addition to their in vivo anti-inflammatory activity. The pyrazoline derivative 9a possessed the highest selectivity index among all compounds regarding COX-2 isozyme (SI = 39) and was almost three folds higher than celecoxib (SI = 13.76) with good in vivo anti-inflammatory activity (% edema inhibition = 11.16–32.64). Compound 10c showed the highest inhibitory activity towards COX-2 isozyme (IC50 = 1.06 μM) and it was the most potent anti-inflammatory derivative (% edema inhibition = 15.04–42.35) with ED50 value of 69.46 μmol/Kg which was approximately one and a half fold more potent than celecoxib (ED50 = 104.88 μmol/Kg). Also, the most potent anti-inflammatory compounds 9a, 9d, 10c and 10d were subjected to ulcerogenic liability and histopathological examinations. Compounds 9d and 10c showed ulcerogenic liability (% ulcerated area = 0.07 and 0.01, respectively) and histopathological changes close to celecoxib. Finally, molecular docking and computational prediction of physicochemical parameters were performed for the prepared compounds to support the biological results.
Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones
Li, Jin-Heng,Li, Yang,Sun, Qing,Xue, Qi,Zhang, Ting-Ting
supporting information, p. 10314 - 10318 (2021/12/17)
A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives. This journal is
Electrochemical Scalable Sulfoxidation of Sulfides with Molecular Oxygen and Water
Cheng, Zhen,Gao, Xinglian,Yao, Lingling,Wei, Zhaoxin,Qin, Guohui,Zhang, Yonghong,Wang, Bin,Xia, Yu,Abdukader, Ablimit,Xue, Fei,Jin, Weiwei,Liu, Chenjiang
, p. 3743 - 3747 (2021/07/26)
An efficient and chemoselective synthesis of sulfoxides through the electrooxidation of sulfides has been well developed. This protocol takes advantage of electricity as the terminal oxidant and of molecular oxygen and water as the oxygen atom sources. A variety of structurally diverse sulfoxide compounds are assembled in moderate to excellent yields. The scaled-up reactions at 6–20 mmol show the good practicability and application potential of this methodology. A possible free radical mechanism has been proposed to rationalize the reaction procedure.
