Chemiluminescence is the emission of safe "cold" light as a result of a chemical reaction. This phenomenon has found diverse applications in environmental and analytical chemistry, and more importantly in diagnostic medicine. Acridinium esters constitute an important class of man-made chemiluminescent materials whose potential still remains to be exploited. Interestingly, while these compounds have been the object of extensive structural modifications, the carbonyl group attached to the crucial position 9 of the acridine ring has never been replaced. The research presented herein is concerned with computational study and design, as well as attempted synthesis, of new acridinium derivatives devoid of a carbonyl group attached to position 9. Part I reviews the most important features of chemiluminescence and its applications in diagnostic medicine (Chapter 1). Part II presents the computational investigation of new acridinium derivatives bearing sulfur-containing groups attached to position 9. While Chapter 2 covers the relevant background aspects of computational chemistry. Chapter 3 presents a study using the two recent semi-empirical molecular orbital methods, AM1 and PM3. This study showed that acridinium-9-thionocarboxylate esters and acridinium-9-sulfonate esters were potentially chemiluminescent and phenyl 10-methylacridinium-9-thionocarboxylate trifluoromethanesulfonate was selected as a synthetic target. Part III details the various approaches to the synthesis of the target thionoester. Chapter 4 gives a general introduction to thionoesters. Chapter 5 describes attempts at direct thionation of phenyl acridine-9-carboxylate and other relevant carboxylic ester derivatives. Chapter 6 presents synthesis of 9-cyanoacridine and attempts at the Pinner reaction followed by sulfhydrolysis as an alternative synthetic route. In Chapter 7m yet another approach is considered, based on the direct esterification of acridine-9-thiocarboxylic acid. In Chapter 8, the reaction of 9-lithioacridine with phenyl chlorothionoformate is investigated.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:638327 |
| Date | January 2001 |
| Creators | Nguyen, C. |
| Publisher | Swansea University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
Page generated in 0.0235 seconds