Syntheses of 14C-labelled (+)-trans-chrysanthemum mono- and di-carboxylic acids, and of related compounds

Crombie, Leslie; Doherty, Christine F.; Pattenden, Gerald

doi:10.1039/j39700001076

Cited by 21 publications

(53 citation statements)

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“…AcOEt and heated under reflux for 2 h. On standing at 25" over night, 13 separated as slightly yellow needles which were filtered off and washed twice with 15 ml of warm AcOEt to yield, after drying at 0.01 Torr, 14.31 g (61.3%) of 13 as colourless needles, m.p. 168.9-170.1" (in agreement with [30]). 07 (m. 1 H);4.50(s,2H);4.02 (d,J = 7.0, 2H);2.1&1.99(m,4H); 1.68, 1.64, 1.60(3s, 9 H).…”

Section: Standard Incubation and Assay Conditionssupporting

confidence: 86%

Regioselectivity and Deuterium Isotope Effects in Geraniol Hydroxylation by the Cytochrome P‐450 Monooxygenase from Catharanthus roseus (L.) G. DON

Fretz

Woggon

1986

Helvetica Chimica Acta

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The hydroxylation of geraniol(8) by cytochrome P-450 (P-450c0,h) from the subtropical plant Catharanthus roseus (L.) G. DON was optimised to give 8-hydroxygeraniol(9) as the single product in 35% yield. Incubations of different I3C-and 2H-labelled geraniols revealed that H-abstraction is completely regioselective in favour of the CH, group trans to the chain at C(6) of 8. An intramolecular isotope effect kH/kD = 8.0 was determined, suggesting that H-abstraction is one of the major rate-contributing steps; however, the intermolecular isotope effect was surprisingly inverse at low conversion kH/kD = 0.50, indicating the existence of rate-contributing steps preceding the first irreversible, isotope-sensitive reaction in the sequence.Introduction. -Cytochrome-P-450-dependent monooxygenases are an ubiquitious class of enzymes which have in common an iron protoporphyrin(1X) substructure in order to bind and activate molecular oxygen (see 1 and 2) [l-31. At present, it is accepted that the bound oxygen is reductively cleaved generating an iron-oxene species (see 3),

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Section: Standard Incubation and Assay Conditionssupporting

confidence: 86%

Regioselectivity and Deuterium Isotope Effects in Geraniol Hydroxylation by the Cytochrome P‐450 Monooxygenase from Catharanthus roseus (L.) G. DON

Fretz

Woggon

1986

Helvetica Chimica Acta

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“…In each photoisomerization reaction there was retention of the (1R)-trans-acid and (1's)-alcohol configurations. The identity of each pyrethrum constituent and of the photoisomers was confirmed by NMR (Bramwell et al, 1969;Crombie et al, 1975;. Purities for the rethrins used in the metabolism studies were established by HRGC-ECD as >96%…”

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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“…The starting materials were prepared by known methods. 1,2) Syntheses of the new compounds. Syntheses of the new norchrysanthemates are summarized in Scheme 1. y To whom correspondence should be addressed.…”

Section: Methodsmentioning

confidence: 99%

“…As a result, a number of synthetic pyrethroids with diverse characteristics have been invented not only for the control of household insect pests, but also for agricultural use. Among these pyrethroids, empenthrin (2) (Fig. 1) is noteworthy for having a high vapor action at room temperature, making it suitable for use as a fumigant in closed spaces to control fabric insect pests in closets.…”

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confidence: 99%

Metofluthrin: A Potent New Synthetic Pyrethroid with High Vapor Activity against Mosquitoes

Ujihara

Mori

Iwasaki

et al. 2004

Bioscience, Biotechnology, and Biochemistry

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(1R)-trans-Norchrysanthemic acid fluorobenzyl esters are synthesized and their structure-activity relationships are discussed. These esters show outstanding insecticidal activity against mosquitoes. In particular, the 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl analog (metofluthrin) exhibits the highest potency, being approximately forty times as potent as d-allethrin in a mosquito coil formulation when tested against southern house mosquitoes (Culex quinquefasciatus). Metofluthrin also exhibits a significant vapor action at room temperature.

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Syntheses of 14C-labelled (+)-trans-chrysanthemum mono- and di-carboxylic acids, and of related compounds

Cited by 21 publications

References 0 publications

Regioselectivity and Deuterium Isotope Effects in Geraniol Hydroxylation by the Cytochrome P‐450 Monooxygenase from Catharanthus roseus (L.) G. DON

Regioselectivity and Deuterium Isotope Effects in Geraniol Hydroxylation by the Cytochrome P‐450 Monooxygenase from Catharanthus roseus (L.) G. DON

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

Metofluthrin: A Potent New Synthetic Pyrethroid with High Vapor Activity against Mosquitoes

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