Search results for "química orgánica"
showing 10 items of 87 documents
Alkane oxidation by a carboxylate-bridged dimanganese(III) complex
2001
[EN] A new manganese( III) oxamato dimer possesing an unprecedented Mn-2(mu -O2CR)(mu -OH2. . .O2CR) core has been synthesised, structurally and magnetically characterised, and used as a catalyst for the oxidation of alkanes to alcohols and ketones by (BuO2H)-O-t and O-2 in CH2Cl2 at rt.
Fluorescent Sensing of Maleate versus Fumarate by a Neutral Cyclohexane Based Thiourea Receptor.
2006
A new cyclohexyl based fluorescent anion receptor, is able to recognize maleate versus fumarate both as their TMA salts. Costero Nieto, Ana Maria, Ana.Costero@uv.es ; Colera Llavata, Manuel, Manuel.Colera@uv.es ; Gaviña Costero, Pablo, Pablo.Gavina@uv.es ; Gil Grau, Salvador, Salvador.Gil@uv.es
DNA damage photo-induced by chloroharmine isomers: hydrolysis versus oxidation of nucleobases
2018
Photodynamic therapy (PDT) is an emerging clinical treatment currently being used against a wide range of both cancerous and noncancerous diseases. The search for new active photosensitizers as well as the development of novel selective delivery systems are the major challenges faced in the application of PDT. We investigated herein three chloroharmine derivatives (6-, 8- and 6,8-dichloroharmines) with quite promising intrinsic photochemical tunable properties and their ability to photoinduce DNA damage in order to elucidate the underlying photochemical mechanisms. Data revealed that the three compounds are quite efficient photosensitizers. The overall extent of photo-oxidative DNA damage i…
Addition of dianions of carboxylic acids to imines. Influence of the acid in the outcome of the reaction
2009
The addition of different carboxylic acids dianions to N-benzylidenebenzeneamine have been studied. The outcome of the reaction depends on the acid. Saturated ones lead to β-aminoacids with good yields and syn-selectivity whereas α,β-unsaturated ones lead to α− and γ− regioisomers with a regioselectivity that depends on the steric hindrance around the reactive centre. From some of these unsaturated acids, polyunsaturated carboxylic acids can be obtained as a change in the reaction conditions lead to the in situ elimination of aniline. From o-methyl aromatic acids δ-aminoacids are isolated with uneven results. Those derived from six member arene carboxylic acids give, on standing, dihydro-2-…
Understanding the participation of 3-nitropyridine in polar Diels–Alder reactions. A DFT study
2015
The reactivity of 3-nitropyridine acting as an electrophilic dienophile in polar Diels-Alder (P-DA) reactions toward three different dienes of increased nucleophilicity has been theoretically studied using DFT methods at the MPWB1K/6-31G(d) level. It has been observed that this aromatic heterocyclic system suffers cycloaddition reactions yielding isoquinoline derivatives. The present DFT study establishes that while the P-DA reactions with isoprene and 1-methoxy-1,3-butadiene take place through a two-stage one-step mechanism, the use of the strong nucleophilic Danishefsky's diene changes the mechanism to a two-step one with formation of a zwitterionic intermediate. These P-DA reactions are …
From over-stoichiometric to sub-stoichiometric enantioselective protonation with 2-sulfinyl alcohols: A view in perspective
2005
A general study of the enantioselective protonation of prochiral enolates with 2-sulfinyl alcohols is reported. The modification of reaction conditions to reduce drastically the amount of chiral proton source needed to obtain a good enantiomeric excess is reported. The effects of the different factors controlling the stereoselectivity are clearly established. Different protocols for enolate generation are compared. Medio Simon, Mercedes, Mercedes.Medio@uv.es ; Aleman Lopez, Pedro Antonio, Pedro.Aleman@uv.es ; Gil Tomas, Jesus Javier, Jesus.J.Gil@uv.es ; Asensio, Aguilar Gregorio, Gregorio.Asensio@uv.es
Weighting non-covalent forces in the molecular recognition of C60. Relevance of concave–convex complementarity
2008
The relative contributions of several weak intermolecular forces to the overall stability of the complexes formed between structurally related receptors and [60]fullerene are compared, revealing a discernible contribution from concave–convex complementarity. Viruela Martin, Pedro Manuel, Pedro.M.Viruela@uv.es ; Viruela Martin, Rafael, Rafael.Viruela@uv.es ; Orti Guillen, Enrique, Enrique.Orti@uv.es
Complexation and Electronic Communication between Corannulene-Based Buckybowls and a Curved Truxene-TTF Donor
2017
Abstract: The association behavior of an electron-donating, bowl-shaped, truxene-based tetrathiafulvalene (truxTTF) with two corannulene-based fullerene fragments, C32H12 and C38H14, is investigated in several solvents. Formation of 1:1 complexes is followed by absorption titrations and complemented by density functional theory (DFT) calculations. The binding constants are in the range logKa=2.9–3.5. DFT calculations reveal that the most stable arrangement is the conformation in which the 1,3-dithiole ring of truxTTF is placed inside the concave cavity of the corannulene derivative. This arrangement is confirmed experimentally by NMR measurements, and implies that a combination of p–p and C…
Conjugated Porphyrin Dimers: Cooperative Effects and Electronic Communication in Supramolecular Ensembles with C60
2016
International audience; Two new conjugated porphyrin-based systems (dimers 3 and 4) endowed with suitable crown ethers have been synthesized as receptors for a fullerene-ammonium salt derivative (1). Association constants in solution have been determined by UV–vis titration experiments in CH2Cl2 at room temperature. The designed hosts are able to associate up to two fullerene-based guest molecules and present association constants as high as ∼5 × 108 M–1. Calculation of the allosteric cooperative factor α for supramolecular complexes [3·12] and [4·12] showed a negative cooperative effect in both cases. The interactions accounting for the formation of the associates are based, first, on the …
Carbon Nanotubes Conjugated with Triazole-Based Tetrathiafulvalene-Type Receptors for C60 Recognition
2019
Fullerene receptors prepared by a twofold CuI -catalyzed azide-alkyne cycloaddition (CuAAC) reaction with -extended tetrathiafulvalene (exTTF) have been covalently linked to singlewalled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs). The nanoconjugates obtained were characterized by several analytical, spectroscopic and microscopic techniques (TEM, FTIR, Raman, TGA and XPS), and evaluated as C60 receptors by UV-Vis spectroscopy. The complexation between the exTTF-triazole receptor in the free state and C60 was also studied by UV-Vis and 1 H NMR titrations, and compared with analogous triazole-based tweezer-type receptors containing the electron-acceptor 11,11,12,12-t…