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Julie N. Ennis
Julie N.
Ennis
Mechanisms and applications of dioxirane chemistry
Loughborough University
2018
untagged
Chemical Sciences not elsewhere classified
2018-05-23 10:48:29
Thesis
https://repository.lboro.ac.uk/articles/thesis/Mechanisms_and_applications_of_dioxirane_chemistry/9397562
Dimethyldioxirane oxidises nitrogen-containing substrates. The sites of oxidation
are generally the sp3 nitrogen atoms in the molecules although other reactive
groups can be oxidised if present. An indication of the reactivity of different
dioxiranes was obtained qualitatively from the polarographic peak reduction
potentials and quantitatively by reaction with the model substrate 4-nitro-N,N-dimethylaniline.
The polarographic peak potentials were shown to be of a similar
order to those of typical acyclic peroxides. The rank order in terms of reactivity
was shown to be methyl(trifluoromethyl)dioxirane > dimethyldioxirane >
ethylmethyldioxirane. The rate of the reaction was not influenced by pH or ionic
strength but was accelerated greatly by the presence of water. An explanation for
this observation was proposed through consideration of dielectric constant and
hydrogen bonding effects. [Continues.]