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Title: Denitrosation and nitrosation : a kinetic and mechanistic investigation
Author: Meyer, Thomas Allan
Awarding Body: Durham University
Current Institution: Durham University
Date of Award: 1981
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Section one of this thesis is concerned with the kinetics and mechanism of the process of denitrosation. At high concentrations of sufficiently reactive nucleophiles the rate of reaction of several N-alkyl-N-nitrosoanilines becomes independent of both the nature and the concentration of such species. This has been intrepreted in terms of a shift in the rate-determining to an earlier one in the reaction pathway, namely the protonation. Support for such a proposal comes from the solvent isotope effects K(_H(_2)O) : K(_D(_2)O) of 1.4 and 0.7, respectively. The denitrosation of D,L-N-acetyl-N-nitrosotryptophan (NANT) has been studied in water in the acid range 4 x 10(^-2) - 1M H(_2)SO(_4) and also at the lower acidities in buffer solution pH 2-6. The reaction was irreversible, giving D,L=N-acetyltryptophan (NAT) and nitrous acid quantitatively. At higher acidities the rate of reaction was independent of added parent amine NAT and also of the addition of various nucleophiles. The kinetic solvent isotope effect k(_H(_2)O) : k(_D(_2)O) was 1.3 and 1.1 at 0.7M H(_2)SO(_4) and 0.1M H(_2)SO(_4), respectively. At pH 6, however, the addition of various nucleophiles did catalyse the reaction, with increasing efficiency along the series C1(^-)
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Chemistry, general Chemistry