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No description available.

No description available.

No description available.

The upgrading of the Norwegian spruce derived bio-oil was carried out in a batch reactor with conditions of 50 bar H2 (cold) and 3 to 13 hr of batch time at 175 to 250 ℃. The emphasis was given on the effect of operating conditions on the hydrodeoxygenation (HDO) performance of unsupported NiMo nano sulphide catalysts. It is found that the degree of deoxygenation of the bio-oil increases and that of hydrogenation of the upgraded products declines with increasing the reaction temperature. The addition of sulphur to prevent the nanosulphide catalyst leaching problem is not essential. Extending the batch time produces more saturated products with less oxygen content, but it can be optimised as the deoxygenation reaction rate decreases along the time. As for HDO solvent, dodecane is preferred comparing with tetralin. The HDO of p-cresol over Co/Al2O3 and Ni/Al2O3 catalysts at 250 to 375 ℃ and 50 bar of H2 (hot) in a batch reactor gives 4-methylcyclohexanol, methylcyclohexane and toluene as the major products. Both catalysts are active leading to almost complete conversion (≥98%) of p-cresol at all temperatures. The degree of deoxygenation and the product distribution of toluene increases with temperature. Toluene can be produced by the direct deoxygenation of p-cresol and by the disproportionation of methylcyclohexenes at high temperature (i.e. 375 ℃). Sulphur suppresses the HDO of p-cresol. It deactivates the hydrogenation sites but does not appear to be a poison for the hydrogenolysis sites. Same conditions were used for the HDO of guaiacol, except the H2 pressure being used was 40 bar (cold). Dominant products are cyclohexanol, methoxycyclohexanols and cyclohexane at 300 ℃ and below and those at 325 ℃ and above are cyclohexane, benzene and ring contraction products (i.e. cyclopentane and methylcyclopentane). High temperatures facilitate deoxygenation and benzene production. As the temperature increases, the methoxyl group is firstly removed and then the hydroxyl group. At 350 ℃, reducing the pressure from 40 bar (cold) to 20 bar (cold) increases the benzene product distribution from 2 wt% to 40 wt%. Sulphur has a detrimental effect on the HDO of guaiacol. Catechol is the main product from guaiacol in the presence of sulphur.

No description available.

En tant qu’alternative aux ressources fossiles, la cellulose se place idéalement pour obtenir des matériaux durables et largement disponibles. Dans le but de respecter les contraintes environnementales, l’efficacité économique et d’être moins préjudiciables à la santé humaine, la technologie plasma non thermique est proposée comme méthode pour la fonctionnalisation et la valorisation des nanocelluloses. Cette technologie ne requiert pas ou peu de réactifs réactionnels, nécessite uniquement un apport énergétique et un flux de gaz. L’élaboration d’un nouveau réacteur a permis la modification de nanocelluloses dispersées en milieu aqueux par la génération d’espèces chimiques hautement réactives à température ambiante. La mise en oeuvre des réactions par plasma en milieu liquide, en utilisant plusieurs solvants aqueux et gaz (N₂, O₂, air, NHᴣ>) a conduit à des fonctionnalisations spécifiques comme oxydation, amination, etc. La grande réactivité du plasma permet l’activation des molécules sans faire appel à des méthodes polluantes ou coûteuses. En raison de son efficacité, sa facilité de mise en oeuvre et de sa faible consommation énergétique, la modification de nanocelluloses par plasma non thermique à pression atmosphérique ouvre de nouvelles voies pour les modifications chimiques de la biomasse. / As an alternative to fossil source, cellulose is ideally placed to obtain sustainable and available materials. In order to respect the environmental constraints, the economic efficiency and to be less detrimental to human health, non-thermal plasma technology is proposed as a method for the nanocellulose functionalization and valorisation. This technology that requires no or few reagents, needs only an energy supply and a gas flow to lead to the modification of nanocellulose by generating highly reactive species at room temperature. The implementation of the reactions by plasma has been carried out in liquid media, using several aqueous solvents and gases (N₂, O₂, air, NHᴣ), their chemical nature allowing access to specific functionalizations such as oxidation, amination, etc. The high reactivity of plasma allows the activation of molecules without using polluting or expensive methods. Because of its efficiency, its ease of implementation and its low energy consumption, the modification of nanocellulose by non-thermal plasma at atmospheric pressure will open new ways to innovative chemical modification of biomass.

Chapter 1 The first section outlines the general approach developed in these laboratories over the past years to the preparation of synthetically useful 6-membered cyclic enamines from their readily available allylamine isomers for use in alkaloid synthesis. The second section provides an estimation of the relative stabilities of some enamine/ allylamine pairs of interest in later chapters by means of molecular orbital calculations. Chapter 2 describes attempts to prepare a synthetically useful 5-membered cyclic enamine from its allylamine isomer in an extension of the Chemistry discussed in Chapter 1. Chapter 3 describes an approach to the synthesis of a model tetracyclic compound with the eventual aim of a total synthesis of one of the alkaloids of the akuammiline group utilising the methodology described in Chapter 1 and modifications suggested from the findings with further model compounds in Chapter 4. Chapter 4 bears a description of a total synthesis of the indole alkaloid deplancheine utilising a previously unknown tetracyclic ketone which was itself prepared simply and efficiently from a protected 3-oxidopyridinium salt by means of a modified form of the general approach discussed in Chapters 1 and 3. Also included is a discussion of an approach to the synthesis of another indole alkaloid, antirhine, from the same tetracyclic ketone. Chapter 5 describes an investigation into the generality and mechanism of formation of some unexpected products derived from complex metal hydride reduction of various 1-substituted-3-oxidopyridiniums. Chapter 6 describes a re-examination of the rearrangement reactions of pyrido-oxepino-indoles previously reported in these laboratories and does indeed confinn the products to be the valuable synthetic intennediate ellipticine quinone and analogues, and further that the rearrangements are entirely regiospecific. Also described are some new short regioselecti ve methods of preparation of the pyridine a.nalogu.es of phthalide required in the pyrido-oxepino-indole syntheses.

This project examines a number of aspects of the development of products for application in industry. This project consists of three parts. The first part investigated optimising an industrial process leading to (S)-4-benzyloxazolidin- 2-one (1). This study has secured a protocol which allows its preparation in high yield and at lower cost. The second part is concerned with the development of a cheap method to access pheromones containing diene, triene and tetraene groups, using acetal (58) derived from the ozonolysis of cyc1onona-l ,4,7 -triene. The third part of the study entails the use of the same Z,Z,Z-cylonona-l,4,7-triene to synthesize novel bis and tris-cyc1ic allenes with eleven and twelve membered rings.

This dissertation describes investigations into novel reactivity modes of strained [nJmetallocenophanes of the late transition metals. Chapter 1 introduces the topic of metallocenes, their structure and bonding and the incorporation of these species into strained [n metallocenophanes. Specific emphasis is placed on the various strain- and redox-induced reactivity modes of ansa metallocenes, including ROP to afford polymetallocenes. Selected examples of the utility of these metal- containing polymers in various applications are also presented. Chapter 2 describes investigations that deduce the mechanism of thermal ring-opening polymerisation (ROP) of dicarba[2Jferrocenophanes as a heterolytic Fe-Cp bond cleavage process. The elucidation of a structure-thermal reactivity relationship for thermally-induced bond cleavage processes of dicarba[2Jferrocenophanes is also discussed. Chapter 3 describes an extension of the studies presented in Chapter 2 to new molecular analogues of dicarba[2Jferrocenophanes and their associated oligo- and polymers. The elucidation of a carbon-carbon bond-cleavage pathway which proceeds in the absence of ring-strain is also detailed. Chapter 4 explores the redox-induced reactivity of [nJruthenocenophanes, including oxidative dirilerization, novel reactivity· modes at the metal centre and a yts _yt3 haptotropic Cp ring slippage with a cyclo-dimerization process. Chapter.S details the ROP of strained [nJnickelocenophanes to afford polynickelocenes, an interesting class of metallopolymers with an S = 1 monomer unit. Investigations of the redox properties of these species will also be presented. Chapter 6 describes the low temperature synthesis of mixed-metal alloy FePd nanoparticles from single-source heterobimetallic [l]ferrocenophane precursors. Analysis of the resulting particles will also be presented. Chapter 7 present: ongoing and potential future avenues of exploration inspired from the results presented within this dissertation.