Idrogenazione selettiva del 5-idrossimetilfurfurale in fase omogenea: studio dell'attività catalitica del complesso di Shvo

Il presente lavoro di tesi è frutto di una collaborazione fra il Dipartimento di Chimica Fisica ed Inorganica (gruppo del Prof. Valerio Zanotti – Mattia Vaccari, Dr. Rita Mazzoni) ed il Dipartimento di Chimica Industriale e dei Materiali (gruppo del Prof. Angelo Vaccari – Dr. Thomas Pasini, Dr. Stefania Albonetti, Prof. Fabrizio Cavani) e si inserisce il un progetto volto a valutare l’attività e la selettività del catalizzatore di idrogenazione di Shvo 1, verso l’idrogenazione selettiva del doppio legame polare del 5-idrossimetilfurfurale (HMF) in fase omogenea. L’HMF è un composto di natura organica facilmente ottenibile dalle biomasse, il quale può essere impiegato come building block per ottenere prodotti ad alto valore aggiunto per la chimica fine o additivi per biocarburanti aventi un elevato potere calorifico. In particolare la nostra attenzione si è rivolta alla produzione del 2,5-diidrossimetilfurano (BHMF), un importante building block per la produzione di polimeri e schiume poliuretaniche. Il lavoro di tesi da me svolto ha riguardato la messa a punto di una nuova metodologia sintetica per la preparazione del catalizzatore di Shvo e lo studio della sua attività catalitica nella riduzione di HMF a BHMF. Il comportamento del catalizzatore è stato monitorato studiando la resa in BHMF in funzione di tutti i parametri di reazione: temperatura, pressione di H2, solvente, rapporto molare substrato/catalizzatore, concentrazione, tempo. Successivamente è stata valutata la possibilità di riciclare il catalizzatore recuperando il prodotto di estrazione con acqua, per precipitazione o eseguendo la reazione in miscela bifasica (toluene/H2O). The present work is a collaboration between the Department of Physics and Inorganic Chemistry (group of Prof. Valerio Zanotti - Mattia Vaccari, Dr. Rita Mazzoni) and the Department of Industrial Chemistry and Materials (Group of Prof. Angelo Vaccari - Dr. Thomas Pasini, Dr. Stefania Albonetti, Prof. Fabrizio Cavani), and it’s a project devoted to evaluate the activity and selectivity of the Shvo catalyst, in the selective hydrogenation of polar double bond of 5 -hydroxymethylfurfural (HMF) in homogeneous phase. The HMF is an organic compound easily obtained from biomass, which can be used as a building block for fine chemicals abd polymer production or additives for biofuels with a high calorific value. In particular, our attention turned to the production of 2.5-bishydroxymethylfuran (BHMF), an important building block for the production of polymers and polyurethane foams. This thesis has involved the development of a new synthetic methodology for the preparation of Shvo’s catalyst and the study of its catalytic activity in the reduction of HMF to BHMF. The behavior of the catalyst was monitored by studying the yield in BHMF as a function of all the reaction parameters: temperature, pressure of H2, solvent, substrate to catalyst molar ratio, concentration, time. Subsequently it was evaluated the possibility of recycling the catalyst recovering the product of extraction with water, by precipitation or performing the reaction in biphasic mixture (toluene/H2O).

Catalizzatori polifunzionali per la sintesi di Metil Isobutil Chetone

In this work, we have examined the activity and selectivity of new catalysts for the single-stage production of methyl isobutyl ketone (MIBK, 4- methyl-2-pentanone) from acetone (both in liquid and gas phase), using a fixed bed reactor operated in the temperature range between 373 and 473 K. The main reaction pathways for the synthesis of MIBK from acetone are given in Fig.1. The first step is the self condensation of acetone to diacetone alcohol (DAA, 4-hydroxy-4-methyl-2-pentanone); the second step is the dehydration of DAA to mesityl oxide (MO, 4-methyl-3-penten-2-one); the final step is the selective hydrogenation of the carbon–carbon double bond of MO to form MIBK. The most commonly observed side reactions are over-condensations and unselective hydrogenations (also shown in Fig.1). Two types of catalysts were studied: i)Pd supported on MgO-SiO2 mixed oxides with ratio of Mg to Si, synthetized using Ohnishi’s method and ii)Pd supported on alumina doped with 5% or 10% of MgO. The different Mg-Si and Mg-Al catalysts were characterized by different techniques (XRD, BET, SEM, NH3-TPD and CO2-TPD) and tested under different conditions in the condensation of acetone to diacetone alcohol and its dehydration to mesityl oxide to enhance the activity. Palladium was chosen as metal component, and its hydrogenation activity was studied. A low hydrogenation activity negatively affects the acetone conversion and promotes the production of mesityl oxide. Hydrogenation conditions being too severe may favor the unwanted hydrogenation of acetone to 2-propanol and of MIBK to methyl isobutyl carbinol (MIBC, 4-methyl-2-pentanol) but this effect is less detrimental to the MIBK selectivity than an unsufficient hydrogenation activity.

Synthesis, Characterization and Conformational Studies of Modified Carbazole-bis-aryl-boranes

During this project we have synthetized different compounds belonging to the class of amino-boranes for the study of bis-aryl-B=N system. We have decided to keep unchanged the aryl components and change only the amine to observe the effect of that on the B=N bond. The used amines are modified carbazoles with functional groups chosen to amplify or disempower the steric and the conjugation effect. We have found that the evaluation of steric barrier was possible studying the gearing aryls rotation around the C-B bonds, while the conjugation barrier is instead given by the energy needed to break the formal double bond B=N and allow the amine rotation. The work started with a proposed synthesis, improved for every reaction, then the products are characterized by NMR, fluorometric spectroscopy, mass spectrometry and X-Ray diffraction on single crystal. The following study on rotational energy barrier was possible theoretically through DFT calculation and experimentally with techniques like Dynamic NMR and EXSY. The fluorometric analysis was done for the study of the solvatochromic propriety of the products.

Synthesis of enantiopure cyclopentanones by desymmetrization of allylic cyclobutanols

The interest in five-membered ring molecules derives from their important application in many different fields, such as pharmaceutical and agrochemical areas. A common strategy for their formation is four-membered ring expansion, which also allows to add molecular complexity and functional handles within one single operation starting from readily available starting materials. Organocatalysis can be exploited to promote the reaction and to obtain a good enantio- and diastereoselection. This technique involves the exclusive use of organic molecules as catalysts, without resorting to metals. The aim of this work is to obtain enantiopure cyclopentanones starting from achiral allylic cyclobutanols. The reaction consists in a ring expansion promoted by the addition of a halogen to the double bond of the substrate, with formation of a haliranium ion as intermediate, followed by a semipinacol rearrangement to afford the cyclopentanone. The reaction is catalysed by a chiral phosphoric acid that, besides accelerating the rate of the reaction, transmits a specific chirality thanks to its chiral structure, following the asymmetric catalysis principles. Starting from symmetric trans-allylic cyclobutanols, the whole reaction is a desymmetrization and leads to the formation of two new stereogenic centres: a mixture of diastereoisomers is obtained, each as couple of enantiomers; the ratio between the possible configurations is determined by the relative position that the chiral catalyst and the reagent occupy during the reaction. Since the reaction is already optimized, the original aim was to study the scope: first, the synthesis of a set of allylic cyclobutanols and their relative precursors, in order to have a wider range of substrates; then, the identification of the type of substrate that undergoes the expansion, with the study of enantio- and diastereoselectivity obtained in each case. Due to the Covid-19 emergency, most of the work was developed as a bibliographic study.

Longitudinal bar buckling behavior

Reinforced concrete columns might fail because of buckling of the longitudinal reinforcing bar when exposed to earthquake motions. Depending on the hoop stiffness and the length-over-diameter ratio, the instability can be local (in between two subsequent hoops) or global (the buckling length comprises several hoop spacings). To get insight into the topic, an extensive literary research of 19 existing models has been carried out including different approaches and assumptions which yield different results. Finite element fiberanalysis was carried out to study the local buckling behavior with varying length-over-diameter and initial imperfection-over-diameter ratios. The comparison of the analytical results with some experimental results shows good agreement before the post buckling behavior undergoes large deformation. Furthermore, different global buckling analysis cases were run considering the influence of different parameters; for certain hoop stiffnesses and length-over-diameter ratios local buckling was encountered. A parametric study yields an adimensional critical stress in function of a stiffness ratio characterized by the reinforcement configuration. Colonne in cemento armato possono collassare per via dell’instabilità dell’armatura longitudinale se sottoposte all’azione di un sisma. In funzione della rigidezza dei ferri trasversali e del rapporto lunghezza d’inflessione-diametro, l’instabilità può essere locale (fra due staffe adiacenti) o globale (la lunghezza d’instabilità comprende alcune staffe). Per introdurre alla materia, è proposta un’esauriente ricerca bibliografica di 19 modelli esistenti che include approcci e ipotesi differenti che portano a risultati distinti. Tramite un’analisi a fibre e elementi finiti si è studiata l’instabilità locale con vari rapporti lunghezza d’inflessione-diametro e imperfezione iniziale-diametro. Il confronto dei risultati analitici con quelli sperimentali mostra una buona coincidenza fino al raggiungimento di grandi spostamenti. Inoltre, il caso d’instabilità globale è stato simulato valutando l’influenza di vari parametri; per certe configurazioni di rigidezza delle staffe e lunghezza d’inflessione-diametro si hanno ottenuto casi di instabilità locale. Uno studio parametrico ha permesso di ottenere un carico critico adimensionale in funzione del rapporto di rigidezza dato dalle caratteristiche dell’armatura.

Synthesis and Characterization of Double Metal Hexacyanoferrates

Manganese Hexacyanoferrate (MnHCF) and nickel doped manganese hexacyanoferrate were synthesized by simple co-precipitation method. The water content and chemical formula was obtained by TGA and MP-AES measurements, functional groups by FT-IR analysis, the crystal structure by PXRD and a local geometry by XAS. Elemental species of cycled samples were further investigated by TXM and 2D XRF. Electrochemical tests were performed in the glass cell. With addition of nickel, vacancies and water content increased in the sample. Crystal structure changed from monoclinic to cubic. Ni disturbed the local structure of Mn, site, however, almost no change was observed in Fe site. After charge/discharge cycling of MnHCF intercalation was already found in the peripheries of charged species after 20 cycle in 2D XRF analysis and randomly distributed intercalated regions after 50 cycles in TXM analysis. Cyclic voltammetry showed that peak-to-peak separation is increasing in case of the addition of Ni to MnHCF.