This Thesis describes some [3,3] and [2,3] -sigmatropic rearrangements that can occur in a variety of polyfluoroaromatic and -heteroaromatic compounds. The presence of fluorine on the aromatic moiety precludes the normal rearomatization process. The work is conveniently divided into two parts. Part A concerns the preparation and thermal (Claisen) rearrangement of derivatives of allyl 5-fluoropyrimidin-4-yl ether. These rearrange upon thermolysis to give isomers in which the terminus for the migration of the allyl group is N-3, provided that there is no preceding reaction which localises a double- bond between C-4 and C-5 - in which case C-5 is the migration terminus. Hydrolysis of some of the N-allyl derivatives results in the formation of some new derivatives of 5-fluorouracil. Part B describes the reactions that occur when polyfluor - inated monocyclic, polycyclic and heterocyclic ring systems are treated with dimethylsulphoxide activated by dicyclohexycarbodi-imide or by trifluoroacetic anhydride. Fluorinated phenolic type compounds give products which are the result of a [2,3] sigmatropic rearrangement of the derived sulphoniumylide. Fluorinated anilines and thiophenols behave differently. Dearomatization occurs under very mild conditions. A number of reactions of the fluorinated cyclohexa-2,4-dienone products are described. The preparation and attempted rearrangement of 2,3,4,5,6- pentafluorobenzylmethylsulphoxide is also discussed.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:373631 |
| Date | January 1986 |
| Creators | Ferguson, John Alasdair Kerr Jamie |
| Publisher | Durham University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://etheses.dur.ac.uk/6870/ |
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