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naturally occurring antineoplastic agent, from the 2-aminophenol derivative
A
(Figure 24).
The kinetics of oxidation of 2-aminophenol (ap) in the presence of [Co
has been interpreted
64
in terms of a mechanism consisting
of the steps shown in Figure 25.
Upon dissolution of the catalyst precursor in MeOH one of the axial
ligands dissociates, generating the active pentacoordinate
catalyst, denoted by The key intermediate is the
superoxocobaloxime derivative which abstracts an H-atom from
the ap substrate
via
an H-bonded species X. The aminophenoxyl radical
produced is further oxidized to -benzoquinone monoimine (bqmi), which is
an intermediate on the path to apx formation. EPR studies provide evidence
for formation of the
free radical as intermediate.
65
4.3
Oxidation of 3,5-di-
tert
-butylcatechol
The
oxidation
of
3,5-di-
tert
-butylcatechol
by
to the
corresponding 1,2-benzoquinone
(DTBQ) is catalyzed by the cobaloxime
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