Thermodynamic values for cation-cyclic polyether interactions for several systems are reported and discussed in light of ligand geometry, cation selectivity, solvent effects, structure, stoichiometry and the nature of the coordinate bond. Cyclic polyethers are shown to be remarkably good ligands even in water and to have marked selectivity for d0, d10 and d10 s2 cations. Syntheses of one new cyclic polyether and several new mixed cyclic polyether-thioethers are reported. Cyclic chelates with smaller rings are shown to prefer smaller cations, but this selectivity is masked by the hydration energy of the cation. Except for thiophillic cations such as Hg2+ and Ag+, substituting sulfur for oxygen in the ligands reduces their complexing power. A large number of crystalline complexes of several cyclic polyethers were isolated containing over twenty different metallic cations. Most had stoichiometries of 1:1 (ligand:metal), but one had 1:2 and several had 2:1 stoichiometries. A unique oxonium complex was also prepared and characterized. A new technique for the separation of crown-31 isomers is outlined.

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The major portion of this work details our investigation of trifluoroethoxy (TFE) substituted compounds with particular emphasis given to their preparation and possible applications. The three types of compounds studied were trifluoroethoxy substituted ketals, enol ethers, and dienol ethers. The ketal and enol ether work involved developing methodology for the large scale preparation of these structures as well as studies detailing their behavior. For the TFE ketals, preparation involved an acid-catalyzed alcohol exchange reaction. Applications included their use as non-complexing/acid-stable carbonyl protecting groups. The TFE enol ether work also involved preparation and applications studies. These structures were synthesized from propargyl ketones via a conjugate addition reaction. The applications were synthetic in nature mainly involving utilization of these compounds in cycloaddition and conjugate addition reactions. The last portion of this work involved our investigation into behavior of trifluoroethoxy substituted dienol ethers (substituted 1-trifIuoroethoxy-3-trialkylsiloxy-1,3- butadienes). Their preparation was accomplished by a method similar to that used by Danishefsky in his synthesis of the 1-methoxy analogs. The applications portion of this study focused on the use of these compounds as 4 carbon synthons in [4+2] cyclcoaddition reactions. Information gained from these studies provided insight into the effect the electron-withdrawing trifluoroethoxy group has on the reactivities of structures into which in has been incorporated. / Ph. D.

Thesis (Ph. D.)--College of William and Mary. / Vita. Includes bibliographical references. Also available via the World Wide Web.

Call number: LD2668 .T4 1962 W33

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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