Acilquinolina y acilfosfina complejos de Rodio (III). Síntesis, caracterización y actividad catalítica

338 p.+ anexos

Prácticas artísticas como procesos sistémicos

Conferencia y debate con Ramón Parramón, Director de ACVIC, Centre d’Arts Contemporànies de Vic (2010), y Director y fundador de IDENSITAT (desde 1999), proyecto colectivo desde el que vehicula su práctica como artista. La sesión estuvo centrada en las distintas facetas que el programa IDENSITAT desarrolla desde su fundación a finales de los 90's, siempre entendiendo como campo de trabajo artístico el territorio social y físico. Por tanto, el cruce disciplinar y profesional para la producción de operativos de intervención social y territorial se explicaron como ejes de trabajo posible para un artista. Ramón Parramón ha dirigido también el Máster en Diseño, Arte y Espacio Público Elisava-UPF (2000-2010). En 2005 fue comisario de Madrid Abierto y de 2005 a 2010 formó parte de su comisión asesora. Ha comisariado varias exposiciones como Artesanos, construcciones colectivas del espacio social (La Capella, Barcelona) Catalizadores (Arts Santa Mònica,Barcelona), Ciudades Intervenidas (La Capella, Barcelona), Apamar: Gráficas, Métricas y Políticas del Espacio (ACVIC). Ha participado y organizado varios seminarios, talleres y foros de debate sobre arte y espacio social. Ha editado varias publicaciones como Mecanismos de Porosidad (EUMO Editorial / ACVIC, 2013), Catalizadores (Arts Santa Mónica / EUMO Editorial, 2010), Acciones Reversibles. Arte, Educación y Territorio (EUMO Editorial / ACVIC, 2010), Local / Visitante. Arte y creación contemporánea en el espacio social (Idensitat, 2010), o Arte, experiencias y territorios en proceso (Idensitat, 2008).

Modelling early transitions toward autonomous protocells.

252 p.

Development of advanced catalytic systems for the selective hydrogenolysis of biomass-derived polyols

195 p.

Foto-oxidación de bisfenol A bajo la acción de luz visible: el monitoreo de oxígeno disuelto como evidencia de la degradación

Propósito y Método del Estudio: El semiconductor más utilizado para su uso en fotocatálisis es el TiO2 debido a sus características como bajo costo, inocuidad y eficiencia fotocatalítica; alguno de los inconvenientes del uso de este material es su capacidad de activarse con radiación UV. En el presente trabajo se modificó al catalizador TiO2 con N a través del método de síntesis coloidal con el propósito de hacerlo fotoactivo bajo radiación visible; se sintetizaron catalizadores modificados a diferentes cantidades teóricas de nitrógeno, los cuales se caracterizaron morfológica y estructuralmente; posteriormente se evaluó la actividad fotocatalítica, bajo radiación visible con una solución de Bisfenol A realizando el seguimiento de la degradación fotocatalítica mediante espectroscopia UV-Vis y cromatografía de líquidos de alta resolución acoplado a espectrometría de masas (HPLC-MS). Contribuciones y Conclusiones: los resultados confirmaron que la incorporación de Nitrógeno al TiO2 provoca cambios en la cristalinidad, morfología y área superficial, así como en su actividad con radiación visible. La evolución fotocatalitica demostró que el catalizador modificado con 5% fue el que presento mayor eficiencia en la degradación de Bisfenol A.

On the reactivity of naphthalene and biphenyl dianions: tying up loose ends concerning an SN2-ET dichotomy in alkylation reactions

Naphthalene and biphenyl dianions are interesting compounds that can be obtained by double reduction of the corresponding arenes in solution with certain alkali metals. These dianions are highly reactive and rather elusive species with very high laying and highly delocalized electrons. They share many aspects of the reactivity of the alkali metal they originated from and consequently behave primarily as strong electron transfer (ET) reagents. We report here kinetic evidence for a different type of reactivity in their alkylation reactions with alkyl fluorides. By using cyclopropylmethyl fluoride (c-C3H5CH2F) as a very fast radical probe, we were able to settle that this alkylation does not involve the classical electron transfer reaction followed by radical coupling between diffusing radicals, but supports the alternative SN2 concerted mechanism, discerning thus this mechanistic SN2-ET dichotomy.

A comparative study of hydroxyl- and carboxylate-functionalized imidazolium and benzimidazolium salts as precursors for N-heterocyclic carbene ligands

The preparation of imidazolium and benzimidazolium salts with hydroxyl or carboxylate functions has been achieved using straightforward synthetic pathways. These salts in combination with palladium(II) acetate give active catalytic systems for Suzuki reaction. A comparative study has been performed, which has revealed that both the heterocycle and the functional group are important for the catalytic activity and stability of the catalyst.

Synthesis of 3,5-Disubstituted Isoxazoles and Isoxazolines in Deep Eutectic Solvents

The synthesis of different 3,5-disubstituted isoxazoles and related isoxazolines using choline chloride:urea as deep eutectic solvent (DES) in a one-pot three step reaction has been accomplished successfully. The use of highly nucleophilic functionalized DES did not affect the process where highly electrophilic reagents or intermediates are involved. The presence of DES showed to be essential since the reaction in absence of this media did not proceed. The DES media could be reused up to five times without a detrimental effect on the yield of the reaction. To exemplify the synthetic potential of this methodology, the reaction was scaled up to the gram scale without any noticeable problem. Finally, different isoxazoles were easily transformed into β-aminoenones.

Reduction of 1,2-dicarbonyl compounds and of their N-phenylimine derivatives by sodium cyanide under aprotic conditions

Some aromatic 1,2-dicarbonyl compounds, i.e. 9,10-phenanthrenequinone, acenaphthenequinone and benzil, and their corresponding N-phenyl monoimines, have been reduced, using dry acetonitrile as the solvent, in the presence of sodium cyanide as a reducing agent. Comparative potentiostatic preparative-scale electrolysis is described.

Direct synthesis of β-ketophosphonates and vinyl phosphonates from alkenes or alkynes catalyzed by CuNPs/ZnO

Copper nanoparticles (CuNPs) supported on ZnO have been shown to effectively catalyze the direct synthesis of β-ketophosphonates from alkenes or alkynes, and that of vinyl phosphonates from alkynes and diethylphosphite, under air and in the absence of any additive or ligand. When using alkynes as starting materials, the selectivity proved to be dependent on the nature of the alkyne. Thus, alkynes conjugated with an aromatic ring or a carbon–carbon double bond gave β-ketophosphonates as the main reaction products, whereas aliphatic alkynes or alkynes conjugated with a carbonyl group led to the formation of the corresponding vinyl phosphonates.

Copper Nanoparticles in Click Chemistry

Conspectus: The challenges of the 21st century demand scientific and technological achievements that must be developed under sustainable and environmentally benign practices. In this vein, click chemistry and green chemistry walk hand in hand on a pathway of rigorous principles that help to safeguard the health of our planet against negligent and uncontrolled production. Copper-catalyzed azide–alkyne cycloaddition (CuAAC), the paradigm of a click reaction, is one of the most reliable and widespread synthetic transformations in organic chemistry, with multidisciplinary applications. Nanocatalysis is a green chemistry tool that can increase the inherent effectiveness of CuAAC because of the enhanced catalytic activity of nanostructured metals and their plausible reutilization capability as heterogeneous catalysts. This Account describes our contribution to click chemistry using unsupported and supported copper nanoparticles (CuNPs) as catalysts prepared by chemical reduction. Cu(0)NPs (3.0 ± 1.5 nm) in tetrahydrofuran were found to catalyze the reaction of terminal alkynes and organic azides in the presence of triethylamine at rates comparable to those achieved under microwave heating (10–30 min in most cases). Unfortunately, the CuNPs underwent dissolution under the reaction conditions and consequently could not be recovered. Compelling experimental evidence on the in situ generation of highly reactive copper(I) chloride and the participation of copper(I) acetylides was provided. The supported CuNPs were found to be more robust and efficient catalyst than the unsupported counterpart in the following terms: (a) the multicomponent variant of CuAAC could be applied; (b) the metal loading could be substantially decreased; (c) reactions could be conducted in neat water; and (d) the catalyst could be recovered easily and reutilized. In particular, the catalyst composed of oxidized CuNPs (Cu2O/CuO, 6.0 ± 2.0 nm) supported on carbon (CuNPs/C) was shown to be highly versatile and very effective in the multicomponent and regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles in water from organic halides as azido precursors; magnetically recoverable CuNPs (3.0 ± 0.8 nm) supported on MagSilica could be alternatively used for the same purpose under similar conditions. Incorporation of an aromatic substituent at the 1-position of the triazole could be accomplished using the same CuNPs/C catalytic system starting from aryldiazonium salts or anilines as azido precursors. CuNPs/C in water also catalyzed the regioselective double-click synthesis of β-hydroxy-1,2,3-triazoles from epoxides. Furthermore, alkenes could be also used as azido precursors through a one-pot CuNPs/C-catalyzed azidosulfenylation–CuAAC sequential protocol, providing β-methylsulfanyl-1,2,3-triazoles in a stereo- and regioselective manner. In all types of reaction studied, CuNPs/C exhibited better behavior than some commercial copper catalysts with regard to the metal loading, reaction time, yield, and recyclability. Therefore, the results of this study also highlight the utility of nanosized copper in click chemistry compared with bulk copper sources.

Recent Advances in the Direct Nucleophilic Substitution of Allylic Alcohols through SN1-Type Reactions

Direct nucleophilic substitution reactions of allylic alcohols are environmentally friendly, since they generate only water as a byproduct, allowing access to new allylic compounds. This reaction has, thus, attracted the interest of the chemical community and several strategies have been developed for its successful accomplishment. This review gathers the latest advances in this methodology involving SN1-type reactions.

In situ characterization of porous VPO catalysts with fibrous structure: Identifying the redox behavior and the stability of active sites

Two VPO materials with fibrillar morphology have been prepared by the aid of electrospinning technique. One is a VPO carbon-supported material (VCF200) with fibrous morphology and very high surface area that is stable under oxidizing conditions up to 350C. The other material is a bulk mixed VPO oxide (VPO500) with fibrous structure obtained after optimizing the calcination of the carbon support in VCF200. Despite it is a bulk oxide material, this material exhibits a high surface area (> 60 m2/g). The redox behavior of both samples was monitored by in situ Raman spectroscopy under oxidation/reduction cycles. For the dehydrated supported sample (VCF200), the pyrophosphate phase (VO)2P2O7 (Raman ~930 cm-1) is detected, which has been described as the active phase (see Figure (a) below). This phase is quite stable since it does not disappear upon subsequent oxidation/reduction cycles. Under reduction conditions at 125C, in consecutive cycles, additional Raman bands appear at ~1090 cm-1 that are characteristic of the αII-VOPO4 phase. On the other hand, the bulk phases show a reversible behavior under redox cycles (Figure (b)). Under reducing conditions, a Raman band appears at ~980 cm-1 (β-VPO phase), whereas under oxidation conditions some segregation to VOx oxides occurs. Nevertheless, this segregation is reversible and the β-VPO phase forms again under reducing conditions. Thus, these results demonstrate that the active VPO phases of these fibrous catalysts are quite stable, and that their structure is reversible under several redox cycles, which make them suitable as oxidation catalysts.