1. Two major metabolites of C-14-labelled (4S, c[(S)-2-methyl-4-oxo-3(
2-propynyl)cyclopent-2-enyl (1R)-trans-chrysanthemate] were purified u
sing a combination of chromatographic techniques and identified by spe
ctroanalysis (nmr(HMBC) and FAB-, TSP-MS). These were established as n
ew types of S-linked conjugates (sulphonic acid and mercapturic acid t
ypes). 2. To examine the mechanism of formation of the sulphonic acid
and mercapturic acid conjugates, sodium sulphate or glutathione labell
ed with S-35 were administered to rat along with unlabelled trans-Etoc
. Both sulphonic acid and mercapturic acid conjugates were found in th
e excreta, more of the former being yielded with S-35-sodium sulphate
than with S-35-glutathione, implying that a sulphonic acid was incorpo
rated into the double bond of a possible intermediate after reduction
of sulphate to sulphite. The mercapturic acid conjugate was produced o
nly with S-35-glutathione, implying incorporation of glutathione into
the triple bond before subsequent generation of mercapturic acid from
the glutathione conjugate. 3. Additional investigation of whether or n
ot the mercapturic acid conjugate was produced by mixing the alcohol m
oiety of Etoc(R) PGL ydroxy-3-methyl-2(2-propynyl)cyclopent-2-en-1-one
) and N-acetyl-L-cysteine under alkaline conditions. However, spectral
data for the synthesized compound were not the same as those of the m
etabolite generated in vivo. That is, the addition reaction appeared t
o proceed by anti-Markownikov's rule, whereas the in vivo metabolite w
as apparently formed according to Markownikov's rule. Addition of glut
athione at a triple bond has not been reported to our knowledge for an
y other foreign compounds in mammalian species.