| Part I. A 1,3,5-triaxial triaminocyclohexane: The triamine corresponding to Keemp's triacid. cis,cis-1,3,5-Triami no- cis,cis-1,3,5-trimethylcyclohexane was prepared from Kemp's triacid by a tris-Curtius rearrangement. X-ray analysis revealed that the three amino groups prefer a triaxial conformation with a "two-protons-plus-one-lone-pair" bifurcated relationship. Several derivatives of Kemp's triacid also prefer triaxial conformation, exhibiting layered structures with hydrophilic facets facing each other. Intramolecular proton transfer and pKa were studied experimentally and theoretically. Several metal complexes---Ni(II), Cu(II), Zn(II) and Co(III) were prepared and characterized by X-ray analysis. Intramolecular proton transfer occurs in the aminolysis of three esters with this triamine. The triamine offers attractive possibilities as a framework for bioorganic modeling.; Part II.{09}Bolaforms with fourteen galactose units: A proposed site-directed cohesion of cancer cells. The synthesis is described of a polyglycosylated bolaform with the following characteristics: (a) To both ends of 16, 21, and 29 atom spacers are placed calixarene rings: (b) Each ring is conjugated to seven galactose derivatives. (c) In addition to the fourteen galactose units, the bis-calixarenes each possess eight undecyl groups. The compounds represent a bolaform version of Aoyama's "monomeric" system (ref. 72) shown to bind effectively to transformed rat liver cells. In synthesizing the bolaforms (whose structure was affirmed by a parent MS signal at mass 8023), conditions were developed that (a) derivatized only one of the eight calixarene hydroxyls and that (b) efficiently derivatized all fourteen of the bolaform hydroxyls. The purpose of constructing these molecules was to develop a "cancer-net" drug which would selectively adhere to, and cross-link, liver cancer cells in order retard cell migration. Although cell experiments did not manifest induced cancer cell floculation (perhaps owing to intracellular looping), the concept remains a viable one that merits further investigation via such functionalized bolaforms and related compounds.; Part III. Vesicular latex. Not a creature from the ocean depths, but the product of synthetic chemistry and lipid self-assembly. The densely packed, hollow spheres with highly blistered surfaces offer the possibility of a useful encapsulation system which is simple, cheap, and endowed with a particularly high capture volume. |
