Synthesis of 9-hydroxy-HEOD, a major mammalian metabolite of HEOD (dieldrin)

Abstract

SuininavyThe first synthesis of a 9-hydroxylated derivative of HEOD (dieldrin) has been accomplished in three steps starting from hexachlorocyclopentadiene and 7-benzoyloxybicyclo [2,2,1]hepta-2,5-diene.

Synthesis of dieldrin metabolites. 3. Two-step conversion of syn-12-hydroxydieldrin into Klein's metabolite (3,5,6,6,7-pentachloro-11,12-exo-epoxypentacyclo[6.4.0.02,10.03,7.05,9]dodecan-4-one)

“…Precedents for such an interaction are scarce, though some are well documented (Capon and McManus, 1976). Howsoever, the availability of syn-12-hydroxydieldrin from our earlier synthesis (Bedford and Harrod, 1972b) and its ready tosylation led quickly to the crucial experiment.…”

“…12-syn-Hydroxydieldrin (Ha) was available from a previous synthesis (Bedford and Harrod, 1972b). The p-toluenesulfonate lib (mp 183-184 °C) and trifluoromethanesulfonate X (mp 136-138 °C) of compound Ha were prepared according to standard procedures (Su et al, 1969).…”

“…In two previous papers on the synthesis of dieldrin metabolites, we have described an improved synthesis of trons-4,5-dihydroaldrin-4,5-diol (Bedford and Harrod, 1972a) and the first total synthesis of syn-12-hydroxydieldrin (Bedford and Harrod, 1972b). In this paper we record a total synthesis of Klein's metabolite and thereby complete the synthesis of all of the known metabolites of dieldrin.…”