The usefulness of imines and iminium salts in the convergent synthesis of alkaloids and their synthetic analogues is described. Thus the anion derived from [3,4-c]pyridin-3[1H]-one, by treatment with LDA (lithium diisopropylamide) or LHS, (lithium bis-trimethylsilylamide) reacts with 2-methyl-3, 4-dihydro- isoquinolinium salts yielding aza analogues of phthalideisoquinoline alkaloids. The condensation of the same anion with 3,4-dihydroisoquinolines has provided, in a single step, azaprotoberberines containing the benzo[a)pyrido[3,4-g]quinolizine structure found in a number of Alangium alkaloids. The reaction of methyllithium with oxoberberine as a means of introducing a methyl group C-8 is described. The resulting iminium salt was reduced to a mixture of racemic a- and B-8-methylcanadines. This reaction has been applied to the synthesis of the Alangium alkaloid (+/-)-alamaridine. Condensation of lithium salts of 3-cyano-4-methylpyridine and 3-cyano-4-methyl-5-vinylpyridine with a complex of 3 ,4-dihydroisoquinolines and trimethylsilyl trifluoromethanesulphonate has been studied. The amidines formed as condensation products were transformed by hydrolysis into 5,6,13,14-tetrahydro-8H-isoquino[2,1-b][2,7]-naphthyridin-8-ones, a ring system found in several alkaloids of Alangtum lamarckii. These reactions have been employed in the synthesis of the Alangium alkaloids, (±)-alangimaridine and alangimarine. The usefulness of this reaction has been further demonstrated in the synthesis of N-benzyl derivatives of 3,14-dihydronauclefine and 3,14-dihydroangustine containing 8,13,13b,14-tetrahydroindolo[2•,3•:3,4]pyrido[1,2-b][2,7]-naphthyridin- 5[7H]-one. / Thesis / Doctor of Philosophy (PhD)

Yes / The design of new functional crystalline materials requires an understanding of the factors that control salt and co-crystal formation. These states often only differ in the location of the proton and are influenced by chemical and crystallographic factors. The interaction between a carboxylic acid and a pyridine is a frequently used supramolecular synthon in crystal engineering which can exist as either a co-crystal (CO2H⋯N) or salt (CO2−⋯HN+). The results of a Cambridge Structure Database search indicate that the nature of the functional groups on the pyridine play a stronger role in selection of the phase than those of the acid. However, the nature of the local hydrogen bonding of the interaction also adjusts the potential for proton transfer. This was demonstrated by ab initio modelling of the energy landscape for binary and ternary co-crystals by inclusion of varying components of the local environment.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1935. / Typescript. With this are bound: The effect of feeding high amounts of soluble iron and aluminum salts / H.J. Deobald and C.A. Elvehjem. Reprinted from American journal of physiology, vol. 111, no. 1 (Feb. 1935), p. 118-123 -- Availability of calcium salts for chicks / by H.J. Deobald, C.A. Elvehjem, E.B. Hart, and J.G. Halpin. Reprinted from Poultry science, vol. XV, no. 1 (Jan. 1936), p. 42-47. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Ph.D. / The specific topic of this investigation is the crystal chemistry and thermotropic polymorphism of the inorganic mineral acid salts of the n-alkyldiamines. This series of compounds contain organic cations with a linear alkane backbone that ranges from short to long chains. As a result their properties changes according to chain length. As they are salts they have the ability to conduct current resulting in wide industrial applications, biological as well as in their use as surfactants and ionic liquids at relatively low temperatures. They also have promising properties for use as propellants, explosives and other pyrotechnic compositions. Their electrical and electronic properties are under investigation. Their ability to exhibit polymorphism has not previously been established. Polymorphism is the ability of a material to exist in more than one crystal form. Since long-chained materials are known to have flexible hydrocarbon chains, by chemical intuition it is reasonable to assume that these materials may have more than one type of molecular arrangement. Various investigations of the conformational and thermotropic polymorphism of the salts of the related n-alkylamines have previously been published in the literature but very little information is available for the polymorphism that may or may not exist in the salts of the n-alkyldiamines. This study is limited to the short and medium chain length n-alkyldiammonium halide salts; nitrate salts; sulphate and perchlorate salts where the general chemical formula for the materials under investigation is CnH2nN+H3X where n = 2 to 12 (except 11) and X = Cl-, Br-, I-, NO3 -, SO4 2- and ClO4 -. It was anticipated that within this range of materials both the hydrogen bonding interactions and the Van der Waal’s forces (as combined packing forces) will play a part in controlling the molecular packing. A large number of the materials were synthesized and their structural information was analyzed by the complimentary techniques of X-ray diffraction and thermal analysis. X-ray diffraction was used in this investigation as it is the best technique to study the crystal chemistry and the polymorphic behaviour of these materials. The results obtained from this method of analysis, the positions of atoms in the crystals, allows for the analysis of the three-dimensional packing in the crystal structure as well as the identification of the hydrogen bonding interactions. The technique of single crystal X-ray diffraction allows the determination of the crystal structures of polymorphs at specific temperatures resulting in information on the effect of change in temperature on crystal packing. Since the compounds investigated in this study were relatively easy to crystallize it was possible to obtain the large single crystals required to obtain single-crystal X-ray diffraction data, and accurate crystal structures could be obtained by this method. Out of a total of thirty-eight crystal structures compared in this investigation, sixteen were novel crystal structures and fourteen were rederminations of previously published structures deemed to be of inferior quality and not suitable for the comparative study. The remaining eight data sets were used as published. Two thermal analytical techniques, Differential Scanning Calorimetry (DSC) and Hot-Stage Microscopy (HSM), were employed to establish if thermotropic phase changes were evident in these materials. Phase transition temperatures at above ambient temperatures were determined by DSC methods while morphological and textural changes in crystals of the compounds under investigation were monitored by HSM methods. In many of the materials analyzed, multiple above ambient phases were identified and only one structure showed a unique below ambient solid-state phase transition.

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published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Brackish waters are now considered valuable alternative water resources. Reverse osmosis (RO) membranes are the most promising candidate for drinking water production through desalination. Low recovery (the fraction of influent water that becomes product water) prevents widespread application of RO inland because of the high cost of waste disposal. The recovery of a brackish RO system is limited by sparingly soluble salts that become supersaturated and precipitate on the membrane surface. Precipitation is controlled through pH adjustment and antiscalant addition; however, at high salt supersaturation, antiscalant control is overcome and precipitation occurs. To further increase RO recovery and avoid precipitation, a three-stage process treated the waste stream (concentrate) of a brackish water RO system through antiscalant degradation, salt precipitation, and solid/liquid separation. Ozone (O3) and hydrogen peroxide (H2O2) were used to degrade antiscalants, pH elevation and base (NaOH/NaHCO3) addition were used to precipitate sparingly soluble salts, and microfiltration (0.1 μm) was used to separate precipitated solids from the water. Optimal parameters (pH, ozone dose, H2O2/O3 ratio, antiscalant type and concentration, water composition) for antiscalant oxidation were determined. The influence of antiscalant type and concentration and pH was investigated for the precipitation and filtration stages. Results were obtained for particle size distribution, extent of precipitation, particle morphology, and particle composition. The effect of ozonation on precipitation and filtration was evaluated, with a comparison to two-stage treatment consisting of precipitation and filtration. Antiscalant oxidation is controlled by bivalent cation coordination, while pH and ozone dose significantly affect the extent of oxidation. The addition of antiscalant prior to precipitation caused changes to particle size and morphology, and results varied with water composition and antiscalant type and concentration. Ozonation, even for small times such as one minute, prior to precipitation and filtration increased calcium precipitation and decomposed the antiscalant enough to remove the effect of the antiscalant on particle characteristics. During ozonation, antiscalants were not completely oxidized, but the partial oxidation products did not seem to affect precipitation. Ozonation also reduced the fouling of microfiltration membranes used for solid/liquid separation. Results indicated concentrate treatment can significantly increase the overall recovery of an RO system. / text