High performance liquid chromatographic separation of the stereoisomers of natural pyrethrins and related compounds.

Ando, Tetsu; Kurotsu, Yuichi; Uchiyama, Masaaki

doi:10.1271/bbb1961.50.491

Cited by 8 publications

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“…Brackets designate compounds tentatively identified from SeO, oxidation and indicated but not established as metabolites. (Ando et al, 1986;McEldowney and Menary, 1988). The E-8'-isomers of JI, CI, and P I were prepared by irradiation for 1 h of the individual natural 2-8'-isomers in degassed n-hexane with ultraviolet light a t 300 nm and purification by HPLC as above with 5% T H F in n-hexane [R, (min) for E isomers of 20.4 for J I , 21.4 for CI, and 24.9 for PI].…”

Section: Methodsmentioning

confidence: 99%

Pyrethroid metabolism: microsomal oxidase metabolites of (S)-bioallethrin and the six natural pyrethrins

Class¹,

Ando²,

Casida³

1990

J. Agric. Food Chem.

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Metabolism of the chrysanthemates (S)-bioallethrin, cinerin I, jasmolin I, and pyrethrin I by NADPHdependent oxidases of mouse liver microsomes yields 13-18 metabolites in each case oxidized a t the methyl, methylene, and alkenyl substituents to form alcohols, aldehydes, carboxylic acids, epoxides, and dihydrodiols. Rat microsomes are more specific than mouse microsomes in hydroxylating the @)-methyl substituent of the 2-methylpropenyl moiety compared with other molecular sites. Metabolites in the urine of allethrin-treated rats include compounds modified in both the 2-methylpropenyl and allyl moieties as free carboxylic acids and glucuronides. The pyrethrates cinerin 11, jasmolin 11, and pyrethrin I1 undergo microsomal hydrolysis of the methoxycarbonyl group and oxidation of the butenyl, pentenyl, and pentadienyl substituents to alcohols, epoxides, and dihydrodiols. Metabolites of these chrysanthemates and pyrethrates are tentatively identified by chemical ionization mass spectrometry following treatment with diazomethane or diazoethane and bis(trimethylsily1)acetamide and separation by high-resolution gas chromatography with hydrogen as the carrier gas.The six natural pyrethrins in pyrethrum extract and their synthetic analogue (SI-bioallethrin (i.e., the rethrins) are important insecticides for control of household and stored products pests (Casida, 1973). The metabolic fates (S)-bioallethrin (A): R, = CH,, R, = H pyrethrin chrysanthemate (I) pyrethrate (11) cinerins (C) CI: R, = CH,, CII: R, = CO,CH,, --R, CH,-R, = CH, R, = CH,CH, R, = CH=CH, jasmolins (J) JI: R, = CH,, JII: R, = CO,CH,, pyrethrins (P) PI: R, = CH,, PII: R, = CO,CH,, R, = CH,CH, R, = CH=CH, of A and PI, partially defined in microsomal oxidase systems and in rats, involve multiple sites of oxidation with little or no cyclopropanecarboxylate hydrolysis (Casida et al., 1971;Elliott et al., 1972). Comparable information is not available on the other pyrethrum constituents except for their relative ease of oxidation in microsomal oxidase systems (Soderlund and Casida, 1977a). With molecules as complex as the rethrins it is difficult to predict the effects of relatively small structural modifications (e.g., R, = CH,, CO,CH,; R2 = H, CH,, CH,CH,, CH=CH,) on their rates and sites of biodegradation. In further evaluating the comparative fate of the rethrins, it is important to use analytical methods applicable to all of the relevant compounds. The pyrethrum constitPresent address:uents and A are conveniently analyzed by high-resolution gas chromatography (HRGC) with an electron-capture detector (ECD) or HRGC-chemical ionization (CI) mass spectrometry (MS). These methods are applied here to the rethrin metabolites, after appropriate derivatizations. This study compares the metabolic fate of A and the six natural pyrethrins in mouse and rat liver microsomal oxidase systems and of A in rats.

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Section: Methodsmentioning

confidence: 99%

Pyrethroid metabolism: microsomal oxidase metabolites of (S)-bioallethrin and the six natural pyrethrins

Class¹,

Ando²,

Casida³

1990

J. Agric. Food Chem.

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“…§ Present address: The Evergreen State College, Olympia, WA 98505. 0021-8561/91/1439-0600$02.50/0 HPLC, for analysis and separation of diastereomers (Ando et al, 1986), used a Beckman 344 gradient liquid chromatograph fitted with a Machrey-Nagel Nucleosil 5 N02 column (10 mm i.d. X 25 cm) (Rainin Instrument Co., Inc., Woburn, MA).…”

Section: Introductionmentioning

confidence: 99%

Epoxychrysanthemates: two-dimensional NMR analyses and stereochemical assignments

Ando¹,

Jacobsen²,

Toia³

et al. 1991

J. Agric. Food Chem.

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Optimized gas chromatographic analysis of natural pyrethrins and pyrethroids

Class

1991

J. High Resol. Chromatogr.

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Gas chromatographic analysis of natural pyrethrins in insecticidal pyrethrum extract and in insecticide formulations is achieved by on‐column injection with hydrogen as carrier gas under constant flow and programmed pressure conditions. Short thin‐film fused silica capillaries (DB 5 and DB 1701) coupled to retention gaps separate the pyrethrins (cinerin I and II, jasmolin I and II, and pyrethrin I and II) and their analogue S‐bioallethrin (Esbiol) in less than twelve minutes at temperatures below 210°C without any discrimination, degradation or isomerization of thermally labile pyrethrin I and II. With S‐bioallethrin added as internal standard, spray and powder formulations are extracted with ethyl acetate and analyzed by gas chromatography with flame ionization detection for pyrethrum constituents, for other pyrethroids such as tetramethrin, cyphenothrin, cypermethrin, and for the commonly used synergist piperonl butoxide.

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High performance liquid chromatographic separation of the stereoisomers of natural pyrethrins and related compounds.

Cited by 8 publications

References 0 publications

Pyrethroid metabolism: microsomal oxidase metabolites of (S)-bioallethrin and the six natural pyrethrins

Pyrethroid metabolism: microsomal oxidase metabolites of (S)-bioallethrin and the six natural pyrethrins

Epoxychrysanthemates: two-dimensional NMR analyses and stereochemical assignments

Optimized gas chromatographic analysis of natural pyrethrins and pyrethroids

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