Chemistry Commons^™

A Novel Synthesis Of Cyclic And Acyclic 3-Alkenoic Acids Via Ionization/Elimination Of Β-Lactones, Stephen Lucas Maluleka

Masters Theses

Exposure of spiro β-lactones and 3-substituted 4,4-dialkyl oxetan-2-ones to magnesium bromide in diethyl ether solvent resulted in the smooth generation of β,γ-unsaturated acid derivatives in high yield and isomeric purity. It is believed that this reaction occurs via the formation of a stable tertiary carbocation at the β-carbon resulting from cleavage of the carbon-oxygen sigma bond due to the complexation of magnesium cation with the ring oxygen atom. Rapid loss of an adjacent proton then furnishes the unsaturated acids. The β-lactone precursors were prepared by the dehydration of β-hydroxy acid derivatives (obtained from the condensation of ketones with acetic acid …

A Spectroscopic Study Of Charge Distribution In Transition Metal Bridging Hydride Complexes, Shixiong Chen

Masters Theses

A series of transition metal bridging hydrides of general formula C[μ-HM₂(CO)₁₀] (C = tetraethylammonium, Et₄N⁺; tetraphenylphosphonium, Ph₄P⁺; of bis(triphenylphosphine)iminium, PPN⁺; M = Cr or W) were synthesized from M(CO)₆ and NaBH₄ bt known methods. As a means of obtaining information about the charge distribution in these complexes, they were allowed to interact in solution and the solid state with triphenylphosphine oxide (TPPO) on the premise that this electron donor could identify sites of relative electron deficiency. Evidence for interaction was sought via solution and …

Derivatization Of Coal By Alkylation And Lithium Iodide Treatment, Cynthia L. Ludwig

Masters Theses

The hypothesis that hydrogen-bonded ethers in coal could be cleaved by reaction with lithium iodide in pyridine to form new phenol groups was investigated for coals #2, 3, and 5 plus their alkylated derivatives from the Argonne Premium Coal Sample Program. Changes caused by alkylation and reaction with LiI were monitored by solvent extraction yeilds, solvent swelling, FT-IR and Size Exclusion Chromatography (SEC).

Solubilities of alkylated coals are rank and oxygen functionality dependent. Evidence supports the hypothesis that the solubilization mechanism is dependent on the extent of hydrogen-bonding in the coal. Elimination of hydrogen-bonds through alkylation increases toluene solubility and …