Formation of diaryl sulfides and sulfoxides: Synthesis,characterization and structure activity correlation studies

Abstract

The synthesis of a series of stable diarylsulfides and sulfoxides is reported. All the newly synthesized compounds were characterized by ¹H, ¹³C NMR and mass spectroscopic techniques. A detailed mechanistic study indicates that the formation of sulfoxides follows the oxidation. In addition to synthesis, characterization and mechanistic studies, the glutathione peroxidase(GPx) mimetic activity of the newly synthesized compounds is described. It is observed that the diaryl sulfides having a heterocyclic ring attached to the nitrogen atom facilitates the oxidation of the sulfur center to form the corresponding sulfoxides. The substituents attached to the nitrogen atom play an important role in the catalytic activity of the substituted diaryl sulfides. The obtained data supports for the higher antioxidant activity of diaryl sulfides than that of the corresponding sulfoxides.     

Studies on the Hydrogen Transfer Reaction Mechanism of Singlet Thiol Phosphinidene Complex and the Temperature Effect

The hydrogen transfer reaction mechanism of the complex of a singlet thiol phosphinidene and a polar molecule hydrogen fluoride (HSP- - - HF) has been investigated at the B3LYP/6-311+G (d,p) level in order to better understand the reactivity of singlet phosphinidene. The results show that the relevant reaction, including step 1 [HSP- - -HF(1) → TS1 (2) → HSPH(F) (3)] and step 2 [HSPH(F) (3) → TS2 (4) → H₂SPF (5)], are very different from the reactions of hydroxyl phosphinidene with hydrogen fluoride. Furthermore, theoretical studies on the thermodynamic and kinetic properties of the reaction have been carried out over the temperature range of 200–1200 K using the DFT/B3LYP method, the general statistical thermodynamics, and Eyring transition state theory with Wigner correction, which is used to examine the temperature effects the reaction channel. It is concluded that step 1 has both thermodynamic and kinetic advantages over step 2, and the high temperature is favorable to step 2. Moreover, the order of lgK and lgk for the steps are consistent with the order of their exoergic energies ΔE and barrier height, but the differences of lgK and lgk for the steps decrease with the temperature increases.     

Manganese‐Catalyzed Cross‐Coupling of Thiols with Aryl Iodides

A manganese‐catalyzed cross‐coupling reaction of thiols with aryl iodides, furnishing aryl thioethers in good to excellent yields has been reported; the system shows good functional group tolerance and enables the sterically demanding aryl iodides to couple with thiols.     

Silica/poly (N‐vinylimidazolium) nanospheres by combined RAFT polymerization and thiol‐ene click chemistry

We report a facile method that combined sol–gel reaction, reversible addition–fragmentation chain transfer (RAFT)/macromolecular design via interchange of the xanthates process and thiol‐ene click reaction to prepare monodisperse silica core‐poly(N‐vinylimidazole) (PVim) shell microspheres of 200 nm in average diameters. First, silica with C = C double bonds was prepared by the sol–gel reaction of 3‐(trimethoxysilyl)propyl methacrylates (MPS) with tetraethoxysilane in ethanol; SiO₂@PVim were subsequently prepared by grafting PVim chain (Mn = 9800 g/mol, polydispersity index = 1.22) to MPS‐SiO₂ via the thiol‐ene click chemisty. The obtained SiO₂@PVim microspheres show higher catalytic activity toward the hydrolysis of p‐nitrophenyl acetate compared with the PVim homopolymers. The as‐prepared composites have been characterized by scanning electron microscopy, transmission electron microscopy, thermal gravimetric analysis and Fourier transform infrared spectrometry analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

Convenient One‐Pot Synthesis of Sulfonamides from Thiols using Trichloroisocyanuric Acid

A convenient synthesis of sulfonamides from thiols is described. In situ preparation of sulfonyl chlorides from thiols is accomplished by oxidation with trichloroisocyanuric acid (TCCA), benzyltrimethylammonium chloride and water (2.5 equiv). The sulfonyl chlorides are then further allowed to react with excess amine in the same reaction vessel. Triethylamine can be optionally added as acid scavenger.     

Thiol peroxidase-like activity of some intramolecularly coordinated diorganyl diselenides

Several new diaryl diselenides having intramolecular coordinating groups have been synthesized by ortho-lithiation/Na2Se2 routes in good yield. Bis[2-(N-phenylferrocenecarboxamide)] diselenide (10), bis[2-(N-tert-butylferrocenecarboxamide)] diselenide (11), (S)(S)-bis[2(-N-phenethylferrocene-carboxamide)] diselenide (12) were synthesized by the ortho-lithiation route. Bis[2-(N,N-dimethyl-aminomethylnaphthyl)] diselenide (13) was synthesized by lithium/bromide exchange reaction whereas bis(2,4-dinitrophenyl) diselenide (14) was prepared by the reaction of disodium diselenide with 2,4-dinitro-1-chlorobenzene. Thiol peroxidase-like activities of the diorganodiselenides have been evaluated by using H₂O₂ as substrate and PhSH as cosubstrate. Diselenides (13) and (14) with dimethylami-nomethyl- or nitro-donor groups in close proximity to selenium, show much better thiol peroxidase-like activities compared to diselenides10–12 with amide donor groups. Cyclic voltammetry study of diselenides10–12 derived from redox-active ferrocenamide has been carried out. Dedicated to the memory of the late Professor Bhaskar G Maiya.     

Sulfur and Its Role In Modern Materials Science

Although well‐known and studied for centuries, sulfur continues to be at the center of an extensive array of scientific research topics. As one of the most abundant elements in the Universe, a major by‐product of oil refinery processes, and as a common reaction site within biological systems, research involving sulfur is both broad in scope and incredibly important to our daily lives. Indeed, there has been renewed interest in sulfur‐based reactions in just the past ten years. Sulfur research spans the spectrum of topics within the physical sciences including research on improving energy efficiency, environmentally friendly uses for oil refinery waste products, development of polymers with unique optical and mechanical properties, and materials produced for biological applications. This Review focuses on some of the latest exciting ways in which sulfur and sulfur‐based reactions are being utilized to produce materials for application in energy, environmental, and other practical areas.     

Bioconjugating Thiols to Poly(acrylamide) Gels for Cell Culture Using Methylsulfonyl Co‐monomers

Poly(acrylamide) P(AAm) gels have become relevant model substrates to study cell response to the mechanical and biochemical properties of the cellular microenvironment. However, current bioconjugation strategies to functionalize P(AAm) gels, mainly using photoinduced arylazide coupling, show poor specificity and hinder conclusive studies of material properties and cellular responses. We describe methylsulfonyl‐containing P(AAm) hydrogels for cell culture. These gels allow easy, specific and functional covalent coupling of thiol containing bioligands in tunable concentrations under physiological conditions, while retaining the same swelling, porosity, cytocompatibility, and low protein adsorption of P(AAm) gels. These materials allow quantitative and standardized studies of cell‐materials interactions with P(AAm) gels.