Dieldrin-14C metabolism in sheep.  Identification of trans-6,7-dihydroxydihydroaldrin and 9-(syn-epoxy)hydroxy-1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro-1,4-endo-5,8-exo-dimethanonaphthalene

Feil, V. J.; Hedde, R. D.; Zaylskie, Richard G.; Zachrison, C. H.

doi:10.1021/jf60167a042

Cited by 37 publications

(8 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The major fecal metabolite (II) was an ideal test for our recently developed method for the pmr analysis of such systems, even though many difficulties have been encountered by previous workers in obtaining interpretable spectra on small amounts of the isolated metabolite. Our spectra of I are essentially identical to those reported by the previous workers (Baldwin et al, 1970a;Feil et al, 1970); however, these workers made no attempt to fully analyze their spectra. The pmr spectrum of II in chloroform-rf contained overlapping signals centered at 7.25 and 7.28, along with a broad signal at 6.45 and an apparent AB quartet centered at r 5.92 and 6.24, with the latter doublet consisting of relatively broad signals indicative of an hydroxyl group.…”

Section: Resultssupporting

confidence: 87%

Major fecal metabolite of dieldrin in rat. Structure and chemistry

McKinney¹,

Matthews²,

Fishbein³

1972

J. Agric. Food Chem.

View full text Add to dashboard Cite

The structure (C-12 jy «-hydroxy dieldrin) of the major fecal metabolite of dieldrin in the rat has been confirmed via pmr spectroscopy employing spin decoupling techniques and the new shift reagent, Eu(DPM)3. Detailed studies of the spectral and reaction properties of this metabolite have established the stereochemical structure and have shown that the system is susceptible to degradation. Evidence is presented which indicates that the major fecal metabolite in the rat cannot be converted to the major urinary metabolite but that a common intermediate hybrid ion (or radical) may exist in their formation from dieldrin. It is proposed that an activated dieldrin molecule may mimic certain male steroidal hormones or their precursors in regard to the capability of anchimeric participation of a double bond. Studiesof the metabolism and other degradative proc-I esses of dieldrin (I) continue to be complicated by difficulties in the unequivocal identification of the transformation products which generally require stereochemical structure proof. This difficulty in making positive structure assignments seems to be primarily due to the lack of substantial spectral and chemical data on related strained model systems. The only metabolite of dieldrin whose structure is unequivocal, having been confirmed by synthesis, is that of Zra«s-4,5-dihydroxy-4,5-dihydroaldrin. [The numbering system used herein for these compounds complies with that suggested by Benson (1969).] Since this metabolite was reported (Korte and Arent, 1965) to possess optical activity, it would be one of the enantiomers of this structure. Recent investigations in our laboratory (McKinney et al., 1971) employing proton magnetic resonance (pmr) spectroscopy including decoupling experiments and sample treatment with the new pmr shift reagent, tris(dipivalomethanato)europium [Eu(DPM)3], enabled the rapid and accurate stereochemical structure determination of some postulated chlorinated polycyclodiene pesticide metabolites.The purpose of this work was to test first the applicability of this pmr method for positive structure assignment of the major fecal metabolite of dieldrin in the rat for which most recent investigators (Baldwin et al., 1970a) have assigned structure II. Secondly, structure confirmation of this metabolite would render its conversion reactions more predictable, and since it is the primary metabolite excreted by the rat, its toxicological meaning in relation to the problems of environmental contamination should be carefully assessed. As a working hypothesis in the chemical studies, it was thought that if the assignment of the position of hydroxylation of dieldrin to the ostensibly aliphatic C-12 methylene group was correct and, if this hydroxyl group had a syn relationship to the epoxide group, conjugation or any other similarly activating derivatization would enable a rather facile rearrangement to occur with the formation of a bridged ketone of identical structure (III) to that proposed (Damico et al., 1968b) for the major urinary metabolite of d...

show abstract

Section: Resultssupporting

confidence: 87%

Major fecal metabolite of dieldrin in rat. Structure and chemistry

McKinney¹,

Matthews²,

Fishbein³

1972

J. Agric. Food Chem.

View full text Add to dashboard Cite

show abstract

“…HEOD (dieldrin) is unchanged by this reaction. The acetate derivatives are converted to the original materials by hydrolysis with 0.5 N alcoholic KOH (10 min at approximately 80°C), thus confirming the presence of a hydroxyl group on metabolite H. An attempt to oxidize metabolite H to an aldehyde or ketone, using the oxidizing mixture described by Feil et al (1970), did not change the rf of metabolite H. The results of the chemical characterization experiments indicate that metabolite H is a monohydroxy derivative of HEOD (dieldrin) with the hydroxyl moiety in a tertiary position. Tissue localization of HEOD (dieldrin) metabolism in the American cockroach.…”

Section: In Vivo Metabolism Of Heod-14c By American Cockroachesmentioning

confidence: 91%

“…1), a metabolite of HEOD (dieldrin), which is known to 230 J.O. Nelson and F. Matsumura form in several biological systems (Korte and Arent t965, Tonflin 1968, Wedemeyer 1968, Matthews and Matsumura 1969, Feil et al 1970). Also identified is metabolite E3 which matches U-1 but is present in only small quantities.…”

Section: In Vivo Metabolism Of Heod-14c By American Cockroachesmentioning

confidence: 99%

Dieldrin (HEOD) metabolism in cockroaches and house flies

Nelson

Matsumura

1973

Arch. Environ. Contam. Toxicol.

View full text Add to dashboard Cite

When carbon-14-1abeled HEOD (dieldrin) is injected into the American cockroach, German cockroach, and house fly, metabolism takes place forming radioactive metabolites which have been isolated and identified by thin-layer chromatographic methods. The major metabolite of dieldrin in the American cockroach is cis-aldrindiol. This is the first report of cis-aldrindiol being formed as a dieldrin metabolite and possible mechanisms for its formation are given. Other dieldrin metabolites identified or characterized indicate that both hydrolytic and oxidative systems are important in the metabolism of dieldrin by the three insect species studied. The in vitro metabolism of HEOD-14C by the fat body from the American cockroach also supports the above conclusion.

show abstract

“…The metabolite designated as A (Figure 1), which was very hydrophilic, was extracted with acetone from TLC plates. Some of it was saved for infrared analysis and the remaining portion was used for acetylation (Feil et al, 1970). Approximately 3000 to 4000 dpm was treated with 0.3 ml of acetic anhydride and 10 m1 of triethylamine.…”

Section: Chemicalsmentioning

confidence: 99%