Synthèse et étude de nouvelles molécules potentiellement polymérisables pour la fabrication de matériaux électroluminescents : analogues du 1,3,5 benzènetripyrrole, méthyle 3,5-bipyrrolebenzoate et 6,12-diméthyle-1,5-dipyrrolediazocane

Pyrroles are found in various natural products and in the chemical composition of certain drugs because of their interesting biological properties. Lipitor, Tolmetin and Amtolmetin are examples of drugs with 1,2,5-substituted pyrroles in their composition, in which biological activities have been certified. Moreover, pyrroles are used as precursors of semiconductor polymers, oligomers and dendrimers useful for the synthesis of electroluminescent materials used in devices, such as organic light-emitting diodes, field-effect transistors, solar and organic photovoltaic cells. We are interested in conjugated polymers based on pyrrole due to their optical properties, electrochemical and the conductivity produced by electron delocalization along their carbon chains. The overall objective of the work presented in this thesis is the synthesis of new molecules based on pyrrole for studying their electronic and electrochemical properties as well for the synthesis of conjugated polymers. Initially, we performed the synthesis of 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes, which may serve as precursors for the synthesis of conjugated dendrimers. Their synthesis was made in three steps starting from trimethyl 1,3,5-benzene-tricarboxylate which was converted to 1,3,5-tri-(pent-4-enoyl)benzene using vinylmagnesium bromide in a Grignard reaction catalyzed by copper cyanide. The olefins of 1,3,5-tri-(pent-4-enoyl)benzene were oxidized to produce 1,3,5-tri-(4-oxopentanoyl)benzene using a modified protocol of the Tsuji-Wacker reaction. Subsequent, Paal-Knorr condensation reactions on 1,3,5-tri-(4-oxopentanoyl)benzene with different amines were used to synthesize 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes with different N-substituents in yields between 44 and 60%. Incomplete reaction of vinylmagnesium bromide with trimethyl 1,3,5-benzenetricarboxylate gave the methyl-3,5-di(pent-4-enoyl)benzoate, which was converted to methyl-3,5-dipyrrolylbenzoate following the reaction of Tsuji- Wacker and Paal-Knorr with yields between 30 and 60%. The photochemical and electrochemical properties of the 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes and methyl-3,5-dipyrrolylbenzoates were studied in collaboration with the research group of professor William Skene. The results have shown that both types of pyrrole have potential for the synthesis of conjugated polymers and dendrimers used in the manufacture of electroluminescent materials. Following these encouraging results, we performed the synthesis of 6,12-dimethyl-1,5-dipyrrolediazocane. Methyl N-(Boc)-β-alaninate was converted to its corresponding homoallylic ketone, which was oxidized to N-(Boc)aminoheptan-3,6-dione. The Paal-Knorr condensation between N-(Boc)aminoheptan-3,6-dione and aminoheptan-3,6-dione hydrochloride gave 6,12-dimethyl-1,5-dipyrrolediazocane in 17% yield. In sum, we have synthesized and characterized seven new molecules, six of them having photochemical and electrochemical properties interesting for the synthesis of conjugated polymers and dendrimers. The latter offering potential as precursor for the conception of compounds of therapeutic interest.

Caractérisation des matériaux latéritiques pour une meilleure utilisation en Afrique

In spite of the fact that the laterite masonry was often used for building, during the colonial period, the laterite rock is rarely studied. To resolve the economic and environmental problems, concerning the concrete or cinder block construction in Africa, this material can be again a local resource. The objective is to determine the hydro-thermo-mechanical properties of laterite rocks linking with the local geological conditions, to investigate the possibilities to be used in construction housing, sufficiently able to resist to limited loads and to give thermal comfort inside. Some preliminary results are presented here.

Traité de mécanique : statique, cinématique, dynamique, hydraulique, résistance des matériaux, chaudières à vapeur, moteurs à vapeur et à gaz. Dynamique et hydraulique / par L. Arnal,...

Collection : Encyclopédie théorique et pratique des connaissances civiles et militaires ; partie 1, livre 8

Traité de mécanique : statique, cinématique, dynamique, hydraulique, résistance des matériaux, chaudières à vapeur, moteurs à vapeur et à gaz. Statique et cinématique / par L. Arnal,...

Collection : Encyclopédie théorique et pratique des connaissances civiles et militaires ; partie 1, livre 8

Traité de mécanique : statique, cinématique, dynamique, hydraulique, résistance des matériaux, chaudières à vapeur, moteurs à vapeur et à gaz. Chaudières à vapeur, moteurs à vapeur et à gaz / par L. Arnal,...

Collection : Encyclopédie théorique et pratique des connaissances civiles et militaires ; partie 1, livre 8

Traité de mécanique : statique, cinématique, dynamique, hydraulique, résistance des matériaux, chaudières à vapeur, moteurs à vapeur et à gaz. Statique graphique et résistance des matériaux / par L. Arnal,...

Collection : Encyclopédie théorique et pratique des connaissances civiles et militaires ; partie 1, livre 8

Cours de construction ; 1re-2e parties, 1-2. Cours de construction destiné aux conducteurs et employés des Ponts et chaussées, agents-voyers, architectes, garde-mines, employés des compagnies de chemins de fer, entrepreneurs, maîtres ouvriers (charpentiers, menuisiers, serruriers, maçons, tailleurs de pierre, etc.), et à toutes les personnes s'occupant de travaux à un titre quelconque. Matériaux de construction et leur emploi / par Gustave Oslet,...

Collection : Encyclopédie théorique et pratique des connaissances civiles et militaires ; partie 1, livre 6

Matériaux pour l'histoire positive et philosophique de l'homme : bulletin des travaux et découvertes concernant l'anthropologie, les temps anté-historiques, l'époque quaternaire, les questions de l'espèce et de la génération spontanée / par Gabriel de Mortillet

1865/09 (A2)-1866/08.

Matériaux pour l'histoire positive et philosophique de l'homme : bulletin des travaux et découvertes concernant l'anthropologie, les temps anté-historiques, l'époque quaternaire, les questions de l'espèce et de la génération spontanée / par Gabriel de Mortillet

1864/09 (A1)-1865/08.