The Proton Magnetic Resonance Spectra of some Chlorinated Polycyclodiene Pesticide Metabolites. Rapid Assessment of Stereochemistry

Abstract

The rapid and accurate determination of the relative stereochemistry of some postulated chlorinated polycyclodiene pesticide metabolites without excessive dependence on chemical methods is described. Proton assignments were made employing the new nuclear magnetic resonance (n.m.r.) shift reagent, Eu(DPM),, which effected the separation of superimposed signals in these systems. The assignments based on coupling constant information and requiring spin decoupling equipment are in good agreement with those obtained from the Eu(DPM), studies. The data presented establishes the relative stereochemistry of these biologically important compounds and demonstrates the utility of one or both approaches in elucidating their overall structures.On d6crit une m6thode rapide et pr6cise de determiner sans d6pendre d'une facon excessive sur des m6thodes chimiques la stCr6ochimie relative de quelques mktabolites postul6s de pesticides de polycyclodienes chlor6s. On a assign6 les diff6rents protons en utilisant, en r.m.n., le r6actif Eu(DPM), qui permet de s6parer les signaux qui seraient par ailleurs superpos6s dans ce systeme. Les attributions faites en se basant sur des constantes de couplage ou n6cessitant I'utilisation d'equipement pour le d6couplage des spins sont en bon accord avec celles d6coulant des Ctudes faites avec Eu(DPM),. Les donn6es pr6sentCes permettent d'6tablir la stkrkochimie relative de ces compos6s biologiquement importants et d6montrent I'utilitC de chacune des mkthodes dans 1'6lucidation des structures.

Fate of dieldrin in radishes

“…Dieldrin (99.7%) and photodieldrin (98%) analytical standards were obtained from the Environmental Protection Agency (Research Triangle, NC). trans-Aldrin diol was synthesized by the H^O* hydrolysis of dieldrin (Korte and Arent, 1965) with the addition of 1,4-dioxane to enhance the yield (Mckinney et al, 1971). Pepsin powder from porcine stomach mucosa with an activity of 1200-2000 units/mg of protein was used as received (Sigma).…”

Formation of polar metabolites from aldrin by pea and bean root preparations

“…Standards. Aldrin and dieldrin used were analytical grade samples obtained from Applied Science Labs, Inc. Dihydroaldrin (DHA), 4-oxo-4,5-dihydroaldrin (aldrin ketone-AK), exo-4-hydroxv-4,5-dihydroaldrin (xAA), endo-4-hydroxy-4,5-dihydroaldrin (nAA), frans-4,5-dihydroxy-4,5-dihydroaldrin (TAD), and cis,exo-4,5-dihydroxy-4,5dihydroaldrin (CAD) were prepared according to published procedures (McKinney et al, 1971) Procedure. Beans (Phaseolus vulgaris, L., Dwarf Horticulture variety) and peas (Pisum sativum, L., Alaska Wilt Resistant variety) were raised and active root preparations were made as reported earlier (Mehendale et al, 1972).…”

Cellular Localization of Dieldrin and Structure–Activity Relationship of Dieldrin Analogues in Dopaminergic Cells

“…cis -Aldrin diol was synthesized using a method adapted from the literature. , Briefly, aldrin (86 mg, 0.24 mmol) was combined with dry ether (6.4 mL), pyridine (0.15 mL), and osmium tetroxide (50 mg, 0.20 mmol). The reaction was stirred for 2 h at room temperature and then allowed to stand overnight in the dark.…”