Search results for "Reaction"
showing 10 items of 6134 documents
The kinetics of the olivine dissolution under the extreme conditions of nano-silica production
2015
Abstract This article addresses the kinetics of the dissolution of olivine for nano-silica production at extreme conditions. The extreme conditions are pH values between −0.7 and 1, temperature between 50 and 90 °C, solid content around 250 g/L and percentage dissolved between 80% and 99%. This work is structured in 3 parts: (1) chemical and mineralogical characterization of the dunites employed; (2) mechanism of the olivine dissolution focusing on the possible resistances to the transport; and (3) determination of the kinetic parameters kT and n. The results shown here demonstrate that: (1) the limiting step of this process is not the diffusion through a silica layer but the surface reacti…
Effect of Lithium Perchlorate on the Kinetics of the Anionic Polymerization of Methyl Methacrylate in Tetrahydrofuran
1999
The kinetics of the anionic polymerization of methyl methacrylate in the presence of lithium perchlorate (LiClO 4 ) are investigated in THF using 1,1-diphenylhexyllithium as initiator in a flow-tube reactor between -30 and 0 °C. The rate constants of propagation determined in the presence of LiClO 4 are lower than those obtained in the absence of the salt, similar to the effect observed for LiCl. For propagation, the reaction order with respect to active center concentration is found to be 0.5 in both cases, which indicates that LiClO 4 does not effectively perturb the aggregation of the enolate ion pair. The formation of various mixed aggregates is proposed. The polydispersity index of the…
Synthesis, characterization and thermal degradation of 8-hydroxyquinoline–guanidine–formaldehyde terpolymer
2007
Abstract Terpolymer (8-HQGF) has been synthesized using the monomers 8-hydroxyquinoline, guanidine, formaldehyde in 1:1:2 molar proportions. The structure of 8-HQGF terpolymer has been elucidated on the basis of elemental analysis and various physicochemical techniques, i.e. UV–Visible, FTIR–ATR and 1 H NMR spectroscopy. Detailed thermal degradation study of the new terpolymer has been carried out to ascertain its thermal stability. Thermal degradation curve is discussed which shows two decomposition steps (265–475 °C and 540–715 °C). Sharp–Wentworth and Freeman–Carroll methods have been used to calculate activation energies and thermal stability. The activation energy ( E a ) calculated by…
Synthesis of rigid ethynyl-bridged polytopic picolinate ligands for MOF applications
2015
Abstract Segmented homopolytopic ligands that consist of a rigid central arylene platform, ethynylene spacers, and terminal chelating picolinate subunits have been synthesized in good yields in a two-step procedure involving a Sonogashira-type cross coupling reaction between the ester methyl 5-bromopyridine-2-carboxylate and several arylacetylenes, followed by hydrolysis of the resulting methyl picolinates. A similar strategy has been employed for the preparation of heteroditopic ligands containing picolinate and a second non-chelating pyridine or benzoate unit. The compounds are potential candidates for organic linkers in metal–organic frameworks (MOFs).
Oxidative (Cross-)Coupling Reactions Mediated by C-H Activation of Thiophene Derivatives by Using Molybdenum(V) Reagents
2014
Oxidative coupling by using molybdenum pentachloride provides fast and modular access to sophisticated thienoacenes in excellent yields. The coupling process can be accomplished with thiophene and benzothiophene derivatives and provides various complex skeletons such as spirocyclic compounds. In this approach, the first cross-coupling reactions with the use of MoCl5 were established and important motifs for semiconducting materials were synthesized.
Fast and Efficient Microwave-Assisted Synthesis of Perylenebisimides
2015
Perylene-3,4,9,10-tetracarboxylic acid bisimides have been widely studied as industrial pigments. Lately, these dyes have drawn considerable attention because of applications as photocatalysts and organic semi-conductors. Here, we report a novel method for fast and efficient synthesis of many different perylenebisimides, based on microwave-assisted reactions.
Synthesis of 2-isoxazolines: enantioselective and racemic methods based on conjugate additions of oximes.
2010
The formation of 3-unsubstituted 2-isoxazolines by means of condensation reactions between α,β-unsaturated aldehydes and oximes proceeds readily in the presence of catalytic amounts of anilinium salts. Mechanistically, the process involves a fast conjugate addition of the oxime and a slower intramolecular oxime-transfer reaction. The rate of oxime transfer was found to correlate with the acidity of the catalyst. This finding enabled us to discover an enantioselective process in which the fragile conjugate-addition product generated in the first stage is rapidly cyclized into the stable isoxazoline under acidic conditions, with conservation of enantiomeric excess. In summary, herein we descr…
Energy Transfer at the Single-Molecule Level: Synthesis of a Donor-Acceptor Dyad from Perylene and Terrylene Diimides
2013
In 2004, we reported single-pair fluorescence resonance energy transfer (spFRET), based on a perylene diimide (PDI) and terrylene diimide (TDI) dyad (1) that was bridged by a rigid substituted para-terphenyl spacer. Since then, several further single-molecule-level investigations on this specific compound have been performed. Herein, we focus on the synthesis of this dyad and the different approaches that can be employed. An optimized reaction pathway was chosen, considering the solubilities, reactivities, and accessibilities of the building blocks for each individual reaction whilst still using established synthetic techniques, including imidization, Suzuki coupling, and cyclization reacti…
Highly selective electrosynthesis of biphenols on graphite electrodes in fluorinated media.
2011
The direct and selective phenol coupling reaction that provides biphenols still represents a challenge in organic synthesis. The recently developed electrosynthesis on boron-doped diamond anodes with fluorinated additives was developed further to allow the application to less-expensive electrodes and fluorinated media. This advanced protocol allows the highly selective anodic phenol coupling reaction on graphite with a broad scope.
A study of the influence of ionic liquids properties on the Kemp elimination reaction
2009
The morpholino-induced elimination of 5-nitrobenzisoxazole into the relevant 2-cyano-4-nitrophenolate has been used as a sample reaction in order to investigate molecular properties of some room temperature ionic liquids. The kinetic study was carried out at 298 K by means of spectrophotometric measurements. Ionic liquids, which differ in both their cation and anion properties, were used as solvent systems. In particular, aliphatic (pyrrolidinium, piperidinium, and ammonium) and aromatic (imidazolium and pyridinium) ionic liquids were used. For aromatic cations, imidazolium ions having different hydrogen-bond donor ability or a different alkyl-chain length were taken into account. The anion…