Search results for "Reaction"
showing 10 items of 6134 documents
Pumice-supported Cu-Pd catalysts: Influence of copper on the activity and selectivity of palladium in the hydrogenation of phenylacetylene and but-1-…
1999
Abstract Pumice-supported copper–palladium catalysts prepared from organometallic precursor have been tested in the hydrogenation of phenylacetylene and in the hydrogenation/isomerization of the but-1-ene. The structure and catalytic behaviour of the bimetallic catalysts depended on the different temperatures of reduction. The presence of CuO or Cu metal in an alloyed state with Pd influenced the two reactions. The system containing CuO is the most active and selective towards the formation of the monoalkene in the hydrogenation of the highly unsaturated hydrocarbon. The system containing Cu partially alloyed with Pd is more active and selective towards the isomerization of the but-1-ene. T…
Structural evolution of Pt/ceria-zirconia TWC catalysts during the oxidation of carbon monoxide
2004
The structural evolution of two Pt/ceria–zirconia catalysts, characterized by different amounts of supported Pt, was monitored by in situ X-ray diffraction during the anaerobic oxidation of CO at different temperatures. In a first phase, oxygen coming from the surface layers of the ceria–zirconia mixed oxide is consumed and no structural variation of the support is observed. After this induction time, bulk reduction of Pt/ceria–zirconia takes place as a step-like process, while the CO2 production continues at a nearly constant rate. This behavior is totally different from that of the metal-free support in similar reaction conditions, that show a gradual bulk reduction. In repeated oxidation…
Understanding the domino reactions of alkyne-tethered N-tosylhydrazones yielding fused polycyclic pyrazoles. An MEDT study
2019
Abstract The domino reactions of alkyne-tethered N-mesylhydrazones yielding fused polycyclic pyrazoles have been studied within the Molecular Electron Density Theory (MEDT). Analysis of the Gibbs free energies indicates that the more favourable reactive path is the one in which the elimination of mesylate anion takes place before the intramolecular [3 + 2] cycloaddition (IM32CA) reaction, which corresponds with the rate-determining step of these domino processes. ELF topological analysis of the bond formation along the IM32CA reaction indicates that in spite of the high activation energy associated to this intramolecular reaction, it shows a pmr-type mechanism characterised by the presence …
A Hybrid Cavitand Made by Capping Permethylated α-Cyclodextrin with Cyclotriveratrylene
2012
A hybrid C 3 -symmetric cavitand 1, in which permethylated α-cyclodextrin (PM α-CDX) is capped with cyclotriveratrylene (CTV), has been prepared in 8 % yield by intramolecular cyclization of a vanillyl alcohol derivative attached to the primary rim of the CDX platform. The reaction proceeds diastereoselectively (dr ≈ 6:1), the chirality of the α-glucopyranosyl units controlling the chirality of the CTV component. Interestingly, in polar solvents, 1 shows self-complexation properties as the primary methoxy groups of the CDX component are directed towards the CTV cavity.
The ionic liquid effect on the Boulton-Katritzky reaction: a comparison between substrates of different structure
2015
The mononuclear rearrangement of heterocycles, also called Boulton–Katritzky reaction, was studied in ionic liquid solution using N-(5-phenyl-1,2,4-oxadiazol-3-yl)-N′-(4-nitrophenyl)-formamidine as substrate. The investigation was carried out using piperidine as basic catalyst and several ionic liquids differing in both cation and anion structure. Kinetic data collected were compared with the ones previously reported using (Z)-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole to have information about the effect due to the different structure of the alkyl chain borne on the substrate. Furthermore, data were analysed on the grounds of polarity, Kamlet–Taft solvent parameters, but taking…
Aggregation processes of perylene bisimide diimidazolium salts
2015
The supramolecular aggregation of three diimidazolium- functionalized perylene bisimides, differing in the alkyl chain length was investigated. These salts form aggregates in solvents like chloroform, dichloromethane, and glycerol. Solvent-, concentration-, and temperature-dependent spectroscopic studies were carried out, evidencing the occurrence of an isodesmic, enthalpy-driven aggregation process, underpinned by p–p stacking and hydrogen bonding. Moreover, dynamic light scattering (DLS) measurements and SEM images revealed that these salts aggregate in chloroform into elongated structures.
Distance Matters: Biasing Mechanism, Transfer of Asymmetry, and Stereomutation in N-Annulated Perylene Bisimide Supramolecular Polymers
2021
International audience; The synthesis of two series of N-annulated perylene bisimides (PBIs), compounds 1 and 2, is reported, and their self-assembling features are thoroughly investigated by a complete set of spectroscopic measurements and theoretical calculations. The study corroborates the enormous influence that the distance between the PBI core and the peripheral groups exerts on the chiroptical properties and the supramolecular polymerization mechanism. Compounds 1, with the peripheral groups separated from the central PBI core by two methylenes and an ester group, form J-type supramolecular polymers in a cooperative manner but exhibit negligible chiroptical properties. The lack of cl…
Self-assembly of fluorescent diimidazolium salts: tailor properties of the aggregates changing alkyl chain features
2016
Searching for new fluorescent organic salts to be used in biomedical and electrochemical field, we conjugated properties of imidazolium salts with the ones of naphthalene diimide core and we obtained some N,N′-bis-(1-alkyl-3-propylimidazolium)naphthalene diimide diiodides. We took into account alkyl chains going from hexyl to dodecyl, as well as hydrogenated and fluorinated alkyl tails. After determination of their thermal behaviour by differential scanning calorimetry, concentration-, and temperature-dependent spectroscopic studies (UV-vis and fluorescence) were performed evidencing the occurrence of isodesmic and enthalpy-driven self-assembly processes. Properties of aggregates were also …
Stopped-Flow and DFT Studies of Proton Transfer and Isomerization of 5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine and Its Related Base 2-(5-Amin…
2001
International audience; A complete kinetic study of pH-dependent isomerization of 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine (HL) and 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (L‘-) in the pH range from −0.5 to +13 in aqueous solution, which spans over 7 orders of magnitude for the pseudo-first-order rates (log k from −4.8 to +2.5), has revealed for the first time the existence of the corresponding conjugate species L- and HL‘. The study has allowed the determination of the acid dissociation constants of HL (pKa) and HL‘ (pKa‘), as well as all of the individual forward and reverse isomerization rates of the acidic (HL/HL‘) and basic (L-/L‘-) forms. Although L…
Unexpected formation of chroman-4-ones during the synthesis of 4-hydroxymethyl-2H-chromenes from 4-aryloxybut-2-yn-1-ols
1986
Abstract The unexpected formation of chroman-4-ones by refluxing 4-aryloxybut-2-yn-1-ols in diethylaniline has been studied, 4-hydroxymethyl-2H-chromene and chroman-4-carboxaldehyde derivatives being established as intennediates.