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published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Electrical and Electronic Engineering / Master / Master of Philosophy

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

No description available.

Effects of several important source-related and operation-related factors on particle formation and growth as well as potential particle and dissolved organic matter removal by alum coagulation are described. Two representative natural water sources, with low turbidities and high concentrations of dissolved organic matter, and one commercially available crystalline silica, with defined characteristics, were employed to establish initial aquatic particle and dissolved organic matter conditions. Six experimental variables utilized for evaluation include initial pH, initial turbidity, applied pre-ozonation dose, alum dose, flocculation time and sedimentation time. A bench-scale experimental apparatus with capabilities of ozonation, coagulation, sedimentation and membrane filtration was employed to conduct a series of selected experiments. Each factor investigated in this research proves to be able to inpart, individually or collectively, statistically significant effects on particle formation and growth during alum coagulation. While the addition of model particles shows significant enhancement in particle growth, it fails to demonstrate significant improvement in the removal of dissolved organic matter. On the contrary, effects of pH and alum dose on particle formation and growth are accompanied by corresponding effects on the removal of dissolved organic matter. Pre-ozonation of dissolved organic matter renders the dissolved organic matter more hydrophilic by increasing the number of carboxylic acid functional groups. This phenomenon can significantly improve or impede particle growth as well as dissolved organic matter removal during alum coagulation, depending on raw water chemistry and other operational factors. Alum coagulation under all of the conditions investigated in this research is demonstrably more effective in removing aquatic humic susbtances with higher apparent molecular weights and fewer carboxylic acid functional groups, as opposed to those with lower apparent molecular weight and more carboxylic acid functional groups. The predominant removal mechanisms were found to occur at the beginning stage of the coagulation process; that is, the rapid mixing period. The remaining dissolved organic matter and humic substances can form significant amounts of trihalomethanes upon reaction with chlorine.

Alkoxy alkyl groups migrate to benzylic carbon when alkyl alkylphenyl ethers are treated with n-butyllithium and potassium t-butoxide. For alkyl 2,6-dialkylphenyl ethers, yields of the rearrangement products range from 45-70%. Rearrangement products are obtained in 10-30% yield from other dimethylanisoles and methylanisoles. The reactions appear to proceed by homolytic cleavage of the alkoxy alkyl group of alkoxybenzyl anions followed by recombination of the resulting radical pair in a different way. The reaction is useful for preparing 2,6-dialkylphenols and their corresponding ethers. The rearrangement can be avoided by using methyl ethers and working at or below room temperature. This was shown by reacting the dianion from methyl 2,6-dimathylanisole with dialkyl sulfates to give methyl 2,6-dialkylanisoles, with a,ω-dihalides to give methoxy[n]metacyclophanes (n = 8-15), dimethoxy[n.n]metacyclophanes (n = 5-10) and trimethoxy[S.S.S]metacyclophane, and with oxidizing agents to yield dimethoxy[2.2]metacyclophane.

One new dianion was prepared and many alkylation and oxidation reactions of this new dianion and several known dianions were carried out. These reactions provide the best synthetic routes to most of the compounds prepared. More specifically, many oxidation products were obtained when 3-methyl-1,4-pentadiene dianion was treated with alkyl bromides. A quantitative yield of substitution product was obtained by reacting this dianion with trimethylsilyl chloride. New compounds obtained by treating this dianion with 1,2-dichloroethane are shown below: The dianion shown below was prepared from 2,5-dimethyl-1,5-hexadiene and Lochmann's base. Many different 2,5-disubstituted 1,5-hexadienes and related compounds were made by treating this dianion with alkyl halides, sulfates and alkyl (alpha),(omega)-dihalides. Attempts to make a cyclic hexapyridyl by treating 2-methyleneallyl dianion with 6,6'-dicyano-2,2'-dipyridyl (see below) apparently failed.

This work involved synthetic approaches to the anti-tumor agent deoxybouvardin. Numerous reactions were explored in an attempt to build an amino acid from an aromatic aldehyde under mild conditions. From these reactions new and useful synthetic methods have been discovered for making α-acylamino alcohols and unsymmetrical imides. Some dehydroamino acids were successfully prepared from aromatic aldehydes and an N-acylphosphorylglycine ester. Progress towards a synthesis of 5- η-thiodeoxybouvardin will also be discussed.