Date of Award

Winter 1984

Project Type


Program or Major


Degree Name

Doctor of Philosophy


A series of bicyclic amidinium salts and tricyclic ammonium salts have been prepared from corresponding tricyclic orthoamides. The spectroscopic data pertaining to these compounds (IR, ('1)H NMR, ('13)C NMR, ('15)N NMR, DNMR) are discussed in terms of relevant stereoelectronic effects and transannular interactions. The synthetic methodology by which these compounds provide routes to selectively protected cyclic triamines is discussed relative to the preparation of selectively functionalized azapodandocoronands and other compounds of interest.

Precedent for the complexation of alkali metal and other cations by selectively modified azapodandocoronands of the 9 ane N(,3) and 12 ane N(,3) type has been established. The symmetrical compounds below have been shown to be effective for complexation of sodium tetraphenylborate in nonpolar solvents. The abilities of these compounds to complex some other cations has also been determined. Lower limit complexation (stability) constants and free energies of activation for decomplexation have been determined for the azapodandocoronands from NMR data. The conformational changes experienced by these ligands upon complex formation are discussed in terms of observed ('13)C NMR chemical shift changes and molecular mechanics force field calculation data for anticipated uncomplexed and complexed conformations.