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Part I Synthesis And Study Of Cyclic Sulfamates Part Ii Investigation Of Endocyclic Nucleophilic Substitution At Tetracoordinate Sulfur(Vi), Martin George Kociolek

Doctoral Dissertations

Part I. 5-Nitro-N-(p-toluenesulfonyl)-1,2,3-benzoxathiazole-2,2-dioxide was synthesized and reacted with various nucleophiles. Nitrogen nucleophiles attacked the exocyclic sulfur atom resulting in cleavage of the tosyl group. This is due in part to the acidity of the parent benzoxathiazole ring. A series of substituted N-H-1,2,3-benzoxathiazole-2,2-dioxides were synthesized and their pK$\sb{\rm a}$ values were determined. An ab initio study was also undertaken on a simple sulfamate model in order to determine the origin of the increased acidity of the cyclic sulfamates, compared to their acyclic analogues. It was determined that the increased acidity was directly affected by the conformation of the neighboring heteroatoms. This …

Part I Synthesis, Functionalization And Metal Complexation Of Polyamine Macrocycles Part Ii Synthesis And Dynamic Nmr Studies Of Bicyclic Ureas, Daniel Cope Hill

Doctoral Dissertations

Part I. The syntheses and characterizations of novel bicyclic tetraamines (shown below) have been accomplished. The complexation of bicyclic tetraamines (R = CH$\sb3)$ with Li$\sp+$ and Na$\sp+$ have been studied by NMR spectroscopy. These tetraamines are strong bases and selective Li$\sp+$ binders. The parent "cross-bridged cyclam" (R = H; X = Y = CH$\sb2)$ was functionalized with a variety of ligating groups containing heteroatoms. Several of the ligands were investigated as possible radiopharmaceutical ($\rm\sp{99m}Tc$) imaging agent precursors.

Syntheses of non-adjacent selectively functionalized tetraazacycloalkanes have also been developed.

Part II. Synthesis and dynamic NMR studies of intramolecular transamidation of bicyclic urea …

I Synthesis And Dynamic Studies Of Bifunctional Compounds Having Potential Intramolecular Interactions Ii Controlled Release Antifouling Coatings: Approaches To Controlled Release Of Gamma-Decanolactone And 2-Hexanoylfuran Into Seawater, Craig Anthony West

Doctoral Dissertations

I. Potentially reactive, bifunctional compounds 1 and 127 have been studied, and both compounds have been found to undergo rapid base-catalyzed degenerate topomerization. The topomerization processes, which in the case of 1 represents a degenerate transamidation and in the case of 127 a degenerate transesterification, have been studied in acetonitrile-d$\sb3$ and D$\sb2$O under a variety of conditions by the DNMR method. In both cases, the presence of a stable tetrahedral anion intermediate can be inferred from analysis of NMR and IR spectra. In the case of 1, the unusually high rate of topomerization can be attributed to the presence of …