Thesis (Ph. D.)--University of Wisconsin--Madison, 1954. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves [157]-[159]).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1948. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Bibliography: leaves [i]-viii.

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The development of the Friedel-Crafts reaction using anhydrous aluminum chloride in the condensation or aromatic hydrocarbons and alkyl or acyl halides has resulted in many new and diversified applications of this reaction, such as the preparation of hydrocarbons, keto acids, acids, ketones, and phenols. Halides of iron, tin, phosphorus, zinc, and other metals, and acids such as phosphoric, sulfuric, and anhydrous hydrofluoric have been found to catalyze a large number of reactions of this type. These same catalysts now find a wide commercial application in the alkylation of paraffins and naphthenes, and other types of reactions, such as isomerization, transfer of radicals, and cracking of petroleum. Although the Friedel-Crafts synthesis is very widely used in organic syntheses because of its high efficiency, very little work has been done toward developing a more economical catalyst. The anhydrous aluminum chloride generally used is wholly or partially consumed in a large number of the reactions, in addition to presenting a difficult corrosion problem. Some work has recently been done by Sachanen and Caesar⁽²⁵⁾ on the catalytic effect of activated clays and the type of silica-alumina catalysts used in the cracking of petroleum, when used in a Friedel-Crafts type reaction. The limited amount of work which has been done so far indicates that it might be economical to use a synthetic silica-alumina type catalyst to replace the anhydrous aluminum chloride in reactions of this type, because it could be used for some time without replacement. The object of this investigation was to determine the feasibility of using different synthetic silica-alumina type catalysts in the condensation of benzene with acetic anhydride to produce acetophenone. / Master of Science

Thesis (Ph. D.)--University of Wisconsin--Madison, 1955. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 171-180).

The original purpose of this investigation was to prepare a series of diketones. However, since considerable difficulty was encountered in the preparation of these diketones, attention was shifted to a study of the Friedel-Craft reactions of phenolic ethers and to the reaction between phenolic ethers and dicarboxylic acids with boron trifluoride as a catalyst.

Stereodivergent and enantiodivergent pathways for the Friedel–Crafts reactions were computationally studied with DFT methods. This study aims to explain recently observed solvent-dependent regioselectivity, and enantioselectivity when cinchona catalyst is used. Deprotonation reaction, Frontier Kohn-Sham orbitals, dual descriptors, Mulliken charges, and Hirshfeld atomic charge for reactant were calculated and analyzed. The most probable position of electrophilic attack and nucleophilic attack in-silico predicted aligns with experimental observations. The calculation of the transition states on the anionic and neutral model in a vacuum show preference for the electrophilic attack in the para position. In comparison to the anionic system, the presence of potassium cation improves ortho/para selectivity and increases the energy barrier. For the key enantioselective step, 12 transition states were calculated which covers 4 representative product such: (R)-ortho, (S)-ortho, (R)-para, and (S)-para. The computational study suggests, that the presence of the cesium cation is essential for the arrangement of the reactant and catalyst in the transition state, which leads to observed selectivity.

La recherche de nouvelles méthodes pour l’acquisition de données physiques et chimiques de réactions en limitant les effet néfastes sur l’Homme est d’une grande importance pour la chimie moderne. L’utilisation de nouveaux outils miniaturisés permet de limiter les quantités de produits chimiques utilisées tout en augmentant la productivité de la recherche. En effet, l’étude de différents paramètres contrôlés simultanément permet d’augmenter le nombre d’expériences pour un temps donné. Malgré tout, cette étape doit être réalisée après détermination au préalable des paramètres clés de la réaction par l’utilisation d’outils haut débit tels que la robotique. Cesdifférents outils sont utilisés pour l’optimisation et la recherche d’une nouvelle voie de synthèse d’une réaction d’intérêt industriel.De plus, pour répondre à l’intérêt de la catalyse hétérogène dans l’industrie pour la séparation facilitée et le recyclage de ces catalyseurs, nous avons développé deux outils miniaturisés. Cesderniers permettent l’étude et l’acquisition de données de réactions chimiques catalysées par des solides. Le développement s’est inscrit en deux étapes : une caractérisation physique des outils puis l’étude d’une réaction modèle industrielle, l’acylation de l’anisole par des catalyseurs de type zéolite. / The search for new methods for the acquisition of physical and chemical reactions by limiting the effect on humans is of great importance for modern chemistry. The use of new miniaturized tools can limit the quantities of chemicals used while increasing research productivity. Indeed, the study of the various parameters monitored simultaneously increases the number of experimentsfor a given time. Nevertheless, this step must be performed after prior determination ofthe key parameters of the reaction by the use of high flow tools such as robotics. These tools are used for optimization and the search for new synthetic pathway of a reaction of industrial interest. In addition, to meet the interests of heterogeneous catalysis in industry for easier separation and recycling of these catalysts, we have developed two miniaturized tools. These allow the study and data acquisition of chemical reactions catalyzed by solid. Development was registeredin two stages : a physical characterization tools and the study of an industrial model reaction, the acylation of anisole with zeolite catalysts.

Carbo- and heterocyclic compounds are of great interest to chemists. Intramolecular cyclization strategies of donor-acceptor (D-A) cyclopropanes and alkylidene malonate monoamides have excellent potential for synthesis as they offer easy access to structurally-diverse compounds. The work described in this thesis accesses the scope of the In(OTf)3-catalyzed cyclization reaction of cyclopropanes and alkylidene malonate monoamides. In(OTf)3-catalyzed reactions of alkenyl and heteroaryl cyclopropyl ketones were examined in the synthesis of functionalized cyclohexenone-based derivatives (Chapter 2). Subsequent efforts to utilize a tandem cyclopropane ring-opening/Friedel-Crafts alkylation sequence of methyl 1-(1H-indolecarbonyl)-1-cyclopropanecarboxylates to prepare functionalized hydropyrido[1,2-a]indole-6(7H)-ones is discussed in Chapter 3. The extension of this tandem protocol towards the total synthesis of (±)-deethyleburnamonine is the subject of Chapter 6. Intramolecular Friedel-Crafts alkylation of N-indolyl alkylidene malonate monoamides was also examined. An In(OTf)3-catalyzed cyclization of substituted methyl 2-(1H-indole-1-carbonyl) acrylates afforded a series of 1H-pyrrolo[1,2-a]indole-3(2H)-ones (Chapter 4), whereas substrates with the indole 2-position blocked provided access to substituted 4H-pyrrolo[3,2,1-ij]quinolin-4-ones (Chapter 5).