Search results for "Radical"
showing 10 items of 1401 documents
Metal‐Free Electrochemical Synthesis of Sulfonamides Directly from (Hetero)arenes, SO2, and Amines
2021
Abstract Sulfonamides are among the most important chemical motifs in pharmaceuticals and agrochemicals. However, there is no methodology to directly introduce the sulfonamide group to a non‐prefunctionalized aromatic compound. Herein, we present the first dehydrogenative electrochemical sulfonamide synthesis protocol by exploiting the inherent reactivity of (hetero)arenes in a highly convergent reaction with SO2 and amines via amidosulfinate intermediate. The amidosulfinate serves a dual role as reactant and supporting electrolyte. Direct anodic oxidation of the aromatic compound triggers the reaction, followed by nucleophilic attack of the amidosulfinate. Boron‐doped diamond (BDD) electro…
Investigations Concerning the Correlation of COX-1 Inhibitory and Hydroxyl Radical Scavenging Activity
2008
The aim was to study the COX-1 inhibiting efficacy in context with hydroxyl radical scavenging properties of compounds bearing a carboxylic acid and ester function, respectively. In general, the acids are more potent radical scavengers than the corresponding esters but there is no clear correlation with their COX-1 inhibiting potencies. A feasible scavenging mechanism of carboxylic acids is discussed.
Comparison of spin density calculation methods for various alkyl-substituted 9,10-anthraquinone anion radicals in the solution phase
1996
EPR and ENDOR spectra were recorded for 2-methyl-9,10-anthraquinone (2-methylAQ), 2-ethylAQ, 2-tertbutylAQ and 2,3-dimethylAQ anion radicals in the solution phase. The EPR spectra were simulated with the help of ENDOR data. The experimental isotropic hyperfine coupling constants (IHFCs) were compared with calculated values from semi-empirical INDO, spin-restricted AM1/CI and B3PW91 density-functional methods. The best computational methods for the IHFCs were the semi-empirical AM1/CI method and the B3PW91 density-functional method with a large basis set.
Influence of the nature of the substrate and of operative parameters in the electrocarboxylation of halogenated acetophenones and benzophenones
2005
Abstract The electrocarboxylation of halogenated acetophenones and benzophenones to the corresponding hydroxycarboxylic acids has been carried out in undivided cell equipped with aluminium sacrificial anode and using 1-methyl-2-pyrrolidinone (NMP) as the solvent. The radical anion generated by the electro-reduction of the aromatic ketone is involved in several competitive reactions which lead to the formation of the target hydroxycarboxylic acid, the corresponding alcohol and pinacol and the de-halogenated parent ketone. If sufficiently negative working potentials are imposed, the latter is reduced to the corresponding carboxylate, pinacol and alcohol. Very different results in terms of sel…
Lauroyl peroxide as thermal initiator of lauryl methacrylate monolithic columns for CEC
2008
The preparation of lauryl methacrylate (LMA)-based monolithic columns for CEC using lauroyl peroxide (LPO) as thermal initiator of polymerization has been investigated. The influence of initiator amount and composition of porogenic solvent on the physical and electrochromatographic properties of the resulting LMA-based monoliths was evaluated. A comparison with LMA-based columns thermally polymerized with AIBN was performed. At a given porogenic solvent composition, LMA stationary phases initiated with LPO showed higher permeabilities and better efficiency values than those prepared using AIBN as initiator. The optimum polymerization mixture found for LPO initiator provided a minimum plate …
Polyreactions in ordered systems: Polymerization of octadecyl methacrylate in monolayers at the gas–water interface
1977
The ultraviolet-initiated polymerization of octadecyl methacrylate (ODMA, octadecyl 2-methyl-2-propenoate) as a monomolecular layer at the gas-water interface was studied. The polymerization was carried out at 27°C at the nitrogen-water interface; air inhibits the polymerization. At 27°C the ODMA monolayer exhibits three different states which were characterized by surface pressure-area diagrams and by surface potential measurements. The ODMA monolayer was polymerized under constant surface pressure in the range between 0 and 10 dyne/cm. The polymerization was followed by recording the contraction of the film. The conversion was determined by comparison of the area per monomer unit during p…
Spherical and rod-like colloids with polymer-brush surfaces
2008
In this paper, we describe a strategy to overcome incompatibility of colloidal particles and polymer coils as well as immiscibility of spherical and rod-shaped nanoparticles. Two new types of model colloids are presented, colloidal nanospheres with hairy surfaces (spherical brushes) and polymacromonomers to represent cylindrical brushes. The spherical brushes are synthesized from polyorganosiloxane-μ-gels of diameter 20 nm by grafting onto anionically prepared polystyrene macromonomers of molecular weight M w=5000 g/mol. On average, each sphere has a surface layer of 200 polymer chains. Compatibility of spherical nanoparticles with polymer coils was probed by turbidity of as-cast films as w…
Synthesis of Processable Inorganic‐Organic Hybrid Polymers Based on Poly(silsesquioxanes): Grafting from Polymerization Using ATRP
2008
Inorganic-organic hybrid polymers have been synthesized utilizing atom transfer radical polymerization (ATRP) from a functionalized poly(methylsilsesquioxane) (PMSSQ) macroinitiator. Different polymeric ATRP initiators were prepared by co-condensation of functionalized trichlorosilanes with methyltrimethoxysilane. Various vinyl monomers have been successfully grafted from these macroinitiators, demonstrating a highly variable synthetic concept, which offers the chance to synthesize a wide spectrum of inorganic-organic hybrid polymers. All synthesized polymers were soluble in various organic solvents. Spin-coating these hybrid materials onto various substrates could produce stable and adhere…
Nanoscale hybrid silica/polymer Janus particles with a double-responsive hemicorona
2015
Abstract We report a versatile large-scale synthesis strategy for hybrid Janus nanoparticles with a silica core and a unilaterally attached polymer corona in a size range below 100 nm. The stimuli-responsive behavior of these nanoparticles with a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) hemicorona is investigated. The synthesis is based on a modified version of the Pickering emulsion polymerization technique in combination with surface-initiated atom transfer radical polymerization (ATRP) in a “grafting from” approach. In a first step, poly(vinyl acetate) (PVAc) latex particles are prepared via Pickering emulsion polymerization. Colloidal stability is provided by 30 nm silica nan…
Cyclodextrins in polymer synthesis: free radical polymerization of cyclodextrin complexes with oxazoline-functionalized vinyl monomers as guest molec…
2000
The synthesis of five new oxazoline functionalized vinyl monomers N-[4-(4′,5′-dihydrooxazol-2-yl)phenyl]acrylamide (3 a), N-[4-(4′,5′-dihydrooxazol-2-yl)phenyl]-2-methylacrylamide (3 b), N-{10-[4-(4′,5′-dihydrooxazol-2-yl)phenylcarbamoyl]decyl}-2-acrylamide (5 a), N-{10-[4-(4′,5′-dihydrooxazol-2-yl)phenylcarbamoyl]decyl}-2-methylacrylamide (5 b) and N-[4-(4′,5′-dihydrooxazol-2-yl)-phenyl]-4-vinylbenzamide (7) is described. With an equimolar amount of 2,6-dimethyl-β-cyclodextrin (DMCD) these monomers formed hydrophilic inclusion complexes 3 a,b-DMCD, 5 a,b-DMCD and 7-DMCD. These complexes were polymerized radically in an aqueous medium. Resulting polymers P-(3 a, b), P-(5 a, b) and P-(7) pre…