1-Aza-2-azoniaallene salts are reactive intermediates that undergo [3+2] cycloaddition with many different types of multiple bonds. For the past several years, the Brewer group has studied the reactivity of these intermediates in intramolecular reactions, and have discovered that these cationic heteroallenes can react through a variety of other, mechanistically distinct, pathways to give different classes of nitrogen heterocycles. For example, prior work in the Brewer group revealed that 1-aza-2-azoniaallene salts could react in an intramolecular [4+2] cycloaddition reaction to give protonated azomethine imine salts containing a 1,2,3,4-tetrahydrocinnoline scaffold. Further study of the scope and limitations of this Diels-Alder-like reaction are described herein. These studies primarily focused on how varying the N-aryl ring and alkene substituents affected the reaction. We discovered that in several instances, the metal mediated reaction did not facilitate the cycloaddition very well, so we searched for alternative ways to facilitate the reaction. We discovered that a non-metallic Lewis acid (TMSOTf) provided very clean products with α-chloroazo compounds. I hypothesized that changing the leaving group adjacent to the azo might further improve the reaction. With this in mind, I developed a technique to prepare α-trifluoroacetoxyazo compounds by treating aryl hydrazones with trifluoroacetoxy dimethylsulfonium trifluoroacetate. This technique is compatible with all types of functional groups including nitro aryl compounds, which gave low yields of the corresponding chloroazo derivatives. Importantly, these α-trifluoroacetoxyazo compounds gave even better cycloaddition results when treated with TMSOTf, and this method is more practical, more environmentally friendly, and greener than the metal mediated technique. This process even returned sterically hindered products in high yield, and provide a dearomatized non-protonated azomethine imine salt, which further verified the proposed mechanism of the [4+2] cycloaddition. Azomethine imines are well known to undergo 1,3-dipolar cycloadditions with alkenes. We wondered if the protonated azomethine imine salts generated by the [4+2] cycloaddition could be used in a subsequent base-mediated [3+2] cycloaddition to generate structurally complex tetra- or pentacyclic products. We were pleased to find that the protonated azomethine imines indeed reacted smoothly with a variety of π-system in the presence of triethylamine to give the corresponding cycloadducts in high yields with moderate to high diastereoselectivities. In an attempt to understand the diastereoselectivity of these [3+2] cycloadditions better, I modeled them computationally.

Les disques optiques numériques sont utilisés par de nombreux organismes, publics ou privés, pour l’archivage de données. Malgré les espoirs fondés dans l’utilisation de ces supports, des pertes d’information ont été observées, parfois après seulement quelques années d’archivage. Cette évolution a été attribuée au vieillissement des disques, sans préjuger des constituants impliqués. Ce travail de thèse visait à identifier les modifications chimiques et physiques résultant de l’application de différentes contraintes (photochimique, thermique ethydrolytique) sur des constituants de disques optiques : substrats de CD-R en polycarbonate, couches enregistrables de types « phtalocyanine » et « azoïque » et vernis de protection. L’étude de ce dernier constituant a permis d’élargir les recherches au cas du Blu-ray Disc. Ces évolutions physico-chimiques ont ensuite été corrélées à des variations des paramètres analogiques et numériques de disques soumis aux mêmes contraintes. L’objectif ultime de ce travail était de mettre en place une méthodologie générale permettant de comprendre l’origine de la perte d’information de disques optiques numériques exposés à des contraintes. / Optical discs are often used by many private or public organizations to archive essential data. For a long time these media were supposed to be reliable. However, a loss of the stored data was highlighted, sometimes only after a few years of storage. This degradation was attributed to the discs ageing, without any identification of the materials involved in this ageing. This work aimed to determine the chemical and physical modifications resulting from the application of different stresses (photochemical, thermal and hydrolytic) on the materials used in optical discs : the CD-R polycarbonate substrates, the recording layers based on phthalocyanines and azo compounds, and the protective layers. The study of this last component allowed us to extend the researches to the case of the Blu-ray Disc. These physico-chemical modifications were then correlated to variations in digital and analog parameters of discs submitted to the same stresses. The ultimate objective of this work was to propose a general method that could help to understand the origin of the loss of information of optical discs submitted to stresses.