The biomimetic oxidation of dieldrin using polyhalogenated metalloporphyrins
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Fumio Hino and David Dolphin
Abstract
Biomimetic oxidation of dieldrin produces the same metabolites as generated in vivo, which suggest a ‘radical oxygen- rebound’ mechanism.
References
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The cooxidant (0.66 mmol) was added with stirring, at room temperature, in ten equal portions every 30 min to a solution of the porphyrin catalyst (0.032 mmol) in 10 ml of solvent (A, B, or C). An hour after the last addition of cooxidant the mixture was poured onto water (50 ml) and CH2Cl2(50 ml). After separation the aqueous phase was extracted with CH2Cl2(2 × 20 ml). The combined organic phases were dried over MgSO4, filtered and concentrated to 1 ml which was applied to a thick layer silica TLC plate and developed with light petroleum–EtOAc (5∶1).
The isolated products had identical NMR and IR spectra to authentic samples..
A solution of dieldrin (0.26 mmol) and Fe(ClO4)2(0.1 mmol) in MeCN (5 ml) was flushed with argon, H2O2(0.1 mmol) in MeCN (0.5 ml) was slowly added over 15 min and the solution was then allowed to stand at room temperature for 1 h. The mixture was then extracted with CH2Cl2(2 × 20 ml) and the products separated by TLC..
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