Browsing by Subject "multicomponent"
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Item Development of Ti-mediated multicomponent syntheses via cycloaddition and insertion reactions(2023-05) Frye, ConnorNitrogen-containing compounds are extremely prevalent in bioactive molecules, dyes, electronics, and other materials. Thus, the development of practical synthetic routes to a diverse library of N-containing compounds is vital. Condensation reactions have been traditionally employed to access highly functionalized N-containing compounds. However, these reactions typically exhibit poor chemoselectivity, and frequently require extensive pre-construction of carbon skeletons. These limitations make the development of metal-mediated or -catalyzed multicomponent reactions from simple starting materials an attractive alternative. Given its high abundance and low-cost, Ti is an excellent candidate for facilitating these reactions. Herein, efforts to develop new Ti-mediated or -catalyzed multicomponent transformations for the synthesis of N-containing organic compounds and N-heterocycles are presented. The modular construction of unsymmetrical α-diimines has been achieved through the diimination of alkynes using Ti imidos, nitrosos, and nitriles. This reaction features a key diazatitanacyclohexadiene intermediate, generated ¬in-situ, that undergoes a series of cycloaddition and retrocyclization reactions. The reactivity of this titanacycle towards other unsaturated substrates and electrophiles has been explored, culminating in the development of a multicomponent method for the synthesis of 1,2-dihydropyrimidines. Finally, a newly developed Ti-catalyzed multicomponent synthesis of 2,3-annulated pyrroles from alkynes, 1,2-cyclononadiene, and azobenzene is presented, and the selectivity of other allenes has been assessed. Importantly, all of these Ti-mediated reactions feature key electrocyclic mechanistic steps, and it is becoming increasingly clear that these are a general feature of titanium’s reactivity that can be exploited for the design of new synthetic methods.Item Modeling of Multicomponent Coatings(2023-05) Larsson, ChristopherThin liquid films play a central role in coating processes and other industrial and natural applications. Efficient optimization of these processes requires an understanding of capillary leveling, Marangoni flow, evaporation, and related phenomena. Although mathematical models are useful for gaining such understanding, it can be difficult to extract physical insight as the number of phenomena considered increases, so simplifying assumptions such as the vertical-averaging (VA) approximation for solute concentration are often employed. In the first part of this work, we examine the performance of the VA approximation for three common evaporation models: constant, one-sided, and diffusion-limited. We find that the formal regime of validity of the VA approximation is inaccurate and strongly depends on the evaporation rate. Furthermore, applying the VA approximation outside of its regime of validity results in drastically different film-height and solute-distribution predictions depending on the evaporation model. Many applications often demand multilayer films where each layer has distinct properties, and this gives rise to additional challenges. It has been experimentally demonstrated that two-layer films in which the layers are miscible can undergo dewetting, but theoretical understanding of this phenomenon is lacking. The second part of this work addresses the mechanisms that may initiate dewetting in miscible two-layer two-component films. It is found that a disparity in initial solute concentration between the film layers drives flows that lead to significant film-height nonuniformities. The third part of this talk focuses on evaporating sessile droplets which are critical to many industrial applications and are also ubiquitous in nature. Two predominant evaporation models have emerged in the literature, one-sided and diffusion-limited, with differing assumptions on the evaporation process. While both models are widely used and their predictions can differ greatly from each other, the physical mechanisms underlying these differences are not yet well understood. For the one-sided model, we derive expressions for the droplet lifetime, show that the evaporation rate is proportional to the droplet surface area, and demonstrate that the contact line is always warmer than the bulk of the droplet. Furthermore, we show that differences in the structure of the evaporation models near the contact line lead to qualitatively different behavior of the apparent contact angles and interface temperature profiles.