The synthesis and chemistry of macrocyclic benzo-linked thioethers and sulfoxides.
Kim, Agnes Soomi
1993
Abstract
In the past twenty years, complexation/coordination chemistry has developed rapidly and several classes of selective ligands have been synthesized and studied. While there have been numerous examples of macrocyclic thioethers studied as binding agents, few examples of polysulfoxides have been studied and no examples of polysulfoxides of known configuration have been examined. The polysulfoxides offer new possibilities for complexing in three dimensional arrays. Systems with three or more sulfoxide functional groups would provide new opportunities to explore selective complexation of anions (S sites) or cations (O sites) based on the highly polarized sulfoxide group. 2,3,7,8,12,13-Hexamethoxytribenzo (b,e,h) -1,4,7-trithionin (cyclotrithiaveratrylene, $\rm Vn\sb3S\sb3$) was the first molecule selected for this study since a known synthesis existed and its structure was determined by X-ray crystallography. Another reason for choosing $\rm Vn\sb3S\sb3$ was the fact that $\rm Vn\sb3S\sb3$ exists in a temperature and solvent dependent equilibrium of two conformers, the crown and saddle forms. Using different reagents and conditions the oxidation of $\rm Vn\sb3S\sb3$ was studied. The mono- and disulfoxide were obtained by oxidation of $\rm Vn\sb3S\sb3$ with $\rm H\sb2O\sb2,\ NaIO\sb4,$ MCPBA, and a modified Sharpless oxidation. The monosulfoxide of $\rm Vn\sb3S\sb3$ was also prepared by a different synthetic route involving dianion formation and closure with thionyl chloride. A more lipophilic analog of $\rm Vn\sb3S\sb3$, 2,3,7,8,12,13-hexabutoxytribenzo (b,e,h) -1,4,7-trithionin, was synthesized and oxidized to the trisulfoxide 2,3,7,8,12,13-hexabutoxytribenzo (b,e,h) -1,4,7-trithionin-5,10,15-trioxide. The complexation ability of the butoxylated trithioether and trisulfoxide (with $\rm Cu\sp{I},\ Mo\sp0,\ Pt\sp{II})$ were compared. It was anticipated that a functionality (hydroxyl) introduced may lend some assistance in the oxidations of the sulfur atoms. Another polythioether 2,3,7,8-tetramethoxydibenzo (b,e) -1,4,7-trithiecin-12-ol containing a hydroxyl group was synthesized and the oxidation was briefly studied. The X-ray crystal structure of 2,3,7,8-tetramethoxydibenzo (b,e) -1,4,7-trithiecin-12-ol was determined and complexes (with $\rm Cu\sp{I},\ Mo\sp0)$ were prepared. Another macrocycle that contained six sulfurs in a twenty-membered ring 2,3,7,8,16,17,21,22-octamethoxytetrabenzo (b,e,l,o) -1,4,7,11,14,17-hexathiacycloeicosane-12,26-diol was also prepared and a crystal structure was determined. These three different systems were examined to investigate the complexing ability of the polythioethers and highly polarized sulfoxide groups and to learn to design selective binding cavities for metals, cations, or anions.Other Identifiers
(UMI)AAI9332106
Subjects
Chemistry, Inorganic Chemistry, Organic
Types
Thesis
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