Biodiesel has come to the forefront of the energy community as a clean-burning, renewable energy that can replace the use of No. 2 Diesel fuel. Tall oil fatty acids, a by-product of the pulp and paper industry, may be utilized as a biodiesel feedstock. This thesis presents an empirical study of the acid-catalyzed esterification of tall oil fatty acids into biodiesel. Under atmospheric conditions, factorial design analysis determined the optimum parameters to be methanol ratio (6:1), sulfuric acid (5%), and temperature (60oC). This reaction was tolerant to water up to 1%. A pseudo-homogeneous second order kinetic model was applied to the reaction at the optimal conditions. The Activation Energy was calculated to be 19.73 kJ/mol with a pre-exponential factor of 23.6. Quality tests were performed under ASTM D 6751-06 to evaluate the final product with tall oil methyl esters having exceptional cold flow properties with a cloud point of -10.7oC.

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Diolefin metathesis, using a Re2O7 catalyst, failed to show a reactivity difference due to conjugation of double bonds. However, the same system allows reaction of pentadiene while not affecting cyclopentene yielding a successful reaction ΓÇô separation scheme for a piperylene concentrate mixture.

This report discusses research which was conducted in two areas: the study of aromatic nucleophilic fluoroalkoxylation assisted via cationic phase transfer catalysis and the study of unsymmetrical vinamidinium salts and their reactions with organometallic reagents. Sodium alkoxides have been successfully used to fluoroalkoxylate activated halo- aryl and heteroaryl substrates under phase transfer catalysis conditions. Optimum reaction conditions incorporated tetra-n-butyl-phosphonium bromide as the catalyst and refluxing toluene as the solvent medium. Different quarternary phosphonium and arrmonium salts have been evaluated as catalysts: also, the effects of activating groups, leaving groups, and nucleophiles have been reported. The reaction of 3-dimethylamino-3-phenyl-prop-2-en-l-ylidendimethyliminium perchlorate with organolithium and Grignard reagents has also been studied in an effort to define the reaction in terms of which electrophilic site of the salt is susceptible to nucleophilic attack to the greatest extent. The results reported reveal that the reaction occurs at the 1-position in all cases producing the α, β-unsaturated ketone after acid hydrolysis. Finally, this report reveals the experimental procedures used as well as the spectral and physical data of all new compounds synthesized. Explanations of the data are offered and recommendations for future research in both areas are given.

Thesis advisor: James P. Morken / This dissertation will present three main projects focusing on the transition metal-catalyzed enantioselective synthesis of secondary organoboronic esters and progress towards the total synthesis of sarcodictyins. In the first project, a palladium-catalyzed enantioselective conjunctive cross-coupling reaction with propargylic electrophiles will be described. The tetra-substituted allenes are isolated with good yield and enantioselectivity and the beneficial effects of alcohol additives are investigated. The second project describes the enantioselective synthesis of ɑ-boryl zinc reagents by a nickel-catalyzed carbozincation reaction. The in situ generated ɑ-boryl zinc intermediate can be trapped by copper-mediated allylations, palladium-catalyzed Negishi cross-couplings, and cerium-mediated halogenation reactions to construct various chiral organoboranes. The synthetic utility of this methodology is showcased by the synthesis of natural products, including bruguierol A, (-)-aphanorphine, and (-)-enterolactone. The mechanism is studied with the assistance of EPR and deuterium-labeling experiments and a catalytic cycle through a Ni(I) intermediate is proposed. The third project depicts a synthetic route to essential precursors in the progress of the total synthesis of sarcodictyins. Various attempts to construct the ten-membered ring core of sarcodictyin have been made, including Sonogashira reaction, Dieckmann condensation, and lithium—halogen exchange process. / Thesis (PhD) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.