Cyanox and Surecide are 4-cyanophenol esters of 0, 0-dimethyl phosphorothioic acid and 0-ethyl phenylphosphonothioic acid, respectively. Metabolism of these compounds in bean plants follows the typical pathway for organophosphorus compounds and in neither case does the nitrile group seem to be involved. There is, however, a remarkable quantitative difference in the rate of metabolism between the two compounds.Cyanox is lost rapidly from treated leaves by volatilization and metabolism, and the half-life is one day or less. In contrast, Surecide is much more persistent; the half-life is estimated to be about two weeks. Moreover, cyanoxon, the toxic metabolite of Cyanox, was detected as a transient intermediate to further degradation products, whereas surecide-oxon was not detected.Perhaps the bean plant has the capacity to degrade surecide-oxon as soon as it is produced or perhaps there is no pathway from Surecide to the oxon in bean plants. Desalkyl compounds and 4-cyanophenol are the major metabolites of both compounds.In neither case does photodegradation seem to play a significant role. Intact Cyanox is absorbed from water culture by bean plants, whereas there is practically no uptake of Surecide under the same conditions. Cyanox also dissipates from soil at a much faster rate than does Surecide, giving 4-cyanophenol and desalkyl compounds, whereas Surecide persists longer and gives practically only 4-cyanophenol as degradation products.
The copulation release pheromone of the azuki bean weevil, Callosobyuchus chinensis L., erectin, was identified by us1) as the mixture of Callosobruchusic acid and several hydrocarbons: 3-methylpentacosane, 11-methylheptacosane, 3-methylheptacosane, 11-methylnonacosane, 13-methylnonacosane, 11, 15-dimethylnonacosane, 13-methylhentriacontane, 9, 13-dimethylhentriacontane and 11, 15-dimethyltritriacontane. The synthesis of the hydrocarbon components will be reported elsewhere, because they are the common components of oviposition marking pheromone of the azuki bean weevil. This paper, therefore, reports the synthesis of Callosobruchusic acid and its biological activity as a part of its structural assignment as (E)-3,7-dimethyl-2octenedioic acid (I). Glc conditions for separation and characterization were: 2 m x 3 mm glass column; Uniport KA (80-100 mesh) as support; 15% DEGS as stationary phase; 70 ml/ min of nitrogen; column temperature, 220C, on Shimadzu GC 6A. Rt is given in min. The synthetic scheme is outlined in Fig. 1. Geranyl acetate (II) was converted via III to a crude mixture containing 46% of IV (Rt, 2.1) and 36% of V (Rt, 3.7) according to Meinwald et al. 2) The mixture was oxidized in acetone with Jones reagent to give an oily product containing 79% of VI as determined by glc of the methyl ester (VIa). A portion was purified by column chromatography.
Prothiophos oxon (S-propyl form) and its S-methyl, ethyl and butyl homologs were poor in vitro inhibitors of acetylcholinesterase (AChE), but the S-propyl and butyl oxons were highly insecticidal to houseflies, and inhibited ACNE in vivo. Evidence indicates that such 5alkyl oxons are converted to unstable intermediates by mixed function oxidase system, which have been oxidized on the sulfur and are more reactive with AChE in the case of the S-propyl and butyl oxons, when more hydrolyzable in the case of the S-methyl and ethyl oxons.
In vitro metabolism of S-(4-chlorophenyl) diethyl phosphorodithioate by rat liver microsomal mixed-function oxidase system gave the metabolites, S-(4-chlorophenyl) S-ethyl ethyl phosphorodithiolate and 4-chlorophenyl diethoxyphosphinyl disulfide, in addition to the oxon. An analytical procedure was developed for analyzing these metabolites which included the derivatization of the unstable phosphinyl disulfide with diazomethane and UV irradiation. Such S-alkyl isomer and phosphinyl disulfide compounds must be considered as the potential bioactive metabolites of thiophosphorus pesticides.
Twelve transformation products from phenthoate (PAP)[(CH30)2P(S)SCH(Ph)000C2H5]were identified by using intact mice, rat lliver subcellular fractions and peracid. Other than those previously reported, five products were newly found: (CH30)2P(0)SCH(Ph)000H by mice and microsome-NADPH system (mfo), CH3S(0)CH(Ph)000H by mice, HOCH(Ph)-000C2H5 by mice, mfo and cytosol, (CH3S)(CH30)P(0)SCH(Ph)000C2H5(PAP S-isomer) by mfo and (CH30)2P(0)SSCH(Ph)000C2H5 (phosphinyl disulfide) by peracid oxidation. Based on the identification of the products, the initial modifications seem to occur in five ways on PAP: i) hydrolysis of carboxy ethyl ester; ii) demethylation; iii) formation of phosphorus oxythionate; iv) cleavage of C-S bond; and v) isomerization. Further modifications result in various products. Twenty-three unidentified metabolites were found. PAP S-isomer by mfo and phosphinyl disulfide by peracid oxidation are considered to be produced in mice, but their instability does not allow their finding.
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