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Title: The interaction of nitric oxide with conjugated dienes
Author: Nicholson, Simon Holland
ISNI:       0000 0004 2718 9798
Awarding Body: Council for National Academic Awards
Current Institution: Kingston University
Date of Award: 1970
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The literature dealing with interaction of the dinitrogen tetroxide-nitrogen dioxide equilibrium mixture, dinitrogen trioxide and nitric oxide, with carbon-carbon multiple bonds has been reviewed in detail, with particular reference to the mechanisms which have been suggested at various times. Aspects of the reactions of nitrosyl and nitryl chloride with olefins relevant to this work, have also been mentioned. The characteristics of the interaction of nitric oxide with a solution of a conjugated diene at moderate temperatures have been found to be the rapid production of a bright blue or green colour solution, associated with a nitroso monomer, followed by evolution of large quantities of molecular nitrogen. Some dienes precipitated thermally unstable, dimeric, nitro-nitroso compounds during the course of the reaction and all the diolefins used gave considerable amounts of brown, viscous oils as the major reaction product. The evidence relating to the structure of the solid and oil products is considered in detail and it is inferred that the latter consisted largely of low molecular weight polymers containing nitro and nitrate groups but complete identification of the components was not possible. From a consideration of the evidence accumulated it is concluded that a free radical mechanism operates during the formation of the afore mentioned compounds. This involves initiation by nitrogen dioxide. The resulting nitro allylic radical can undergo several reactions; combination with nitric oxide to give a nitro-nitroso monomer, which disproportionates nitric oxide into molecular nitrogen and nitrogen trioxide via unconfirmed intermediate; reaction with diene monomer and thus leading to polymerisation; addition of nitrogen dioxide or nitrogen trioxide to give dinitro and nitro-nitrate compounds respectively. Since in many cases the products could not be separated in a pure state, extensive use was made of spectroscopic methods of analysis and the interpretation of these results are explained where relevant.
Supervisor: Not available Sponsor: B.P. Chemicals
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available