* A series of investigations has been carried out on multicyclic organic systems. The Ritter Reaction was used to obtain bridged imines containing an azacyclohexene functionality. The crystal structure of the benzene inclusion compound of one of these was determined, and also that of another spontaneously oxidised example. The reactivity of these bridged imines was then investigated using mercaptoacetic acid, and also dimethyl acetylenedicarboxylate (DMAD). The three bridged imines studied were found to react with DMAD in totally different ways and produced most unusual products whose structures were proved using X-ray crystallography. Mechanistic explanations are provided for the formation of these novel and totally unexpected products. * 6-Methylidene-3,3,7,7-tetramethylbicyclo[3.3.1]nonan-2-one was reacted with acetonitrile and sulfuric acid to deliberately combine molecular rearrangement with Ritter Reaction chemistry. Five different products were obtained and the pathway of formation of these products was uncovered. The structures of three of these rearranged substances were confirmed by X-ray methods. * The rare tricyclo[5.3.1.1 3,9]dodecane ring system is known to contain severe skeletal distortions due to the nature of its skeleton. These properties were investigated by means of X-ray determinations at two temperatures. It was found that although the bond lengths were little affected, several of the bond angles were highly anomalous. These had angles far from the ideal tetrahedral value and, in some cases, were close to planar (120 degrees). The molecular motion of the skeleton was also investigated using variable temperature NMR measurements and energy values for the twisting motion involved were determined. * Schroeter and Vossen's Red Salt, first discovered in 1910, was investigated in detail by NMR and X-ray spectroscopy. The detailed structure of this most unusual compound was determined for the first time. * The Red Salt is based on the bicyclo[3.3.0]octane ring system and can be converted into several synthetically useful derivatives, including a tetraester and the 3,7-diketone. The former was shown to exist completely in the enolised tautomeric form (like Meerwein's Ester), and the latter was used as a synthetic entry for making diquinoline substituted analogues of interest in host-guest chemistry.
| Identifer | oai:union.ndltd.org:ADTP/234787 |
| Date | January 2006 |
| Creators | Al Djaidi, Djamal Sholeh, Chemistry, Faculty of Science, UNSW |
| Publisher | Awarded by:University of New South Wales. School of Chemistry |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | Copyright Djamal Sholeh Al Djaidi, http://unsworks.unsw.edu.au/copyright |
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