Photodegradation of insecticide metofluthrin on soil, clay minerals and glass surfaces

Nishimura, Hirokazu; Suzuki, Yusuke; Nishiyama, Masahiro; Fujisawa, Takuo; Katagi, Toshiyuki

doi:10.1584/jpestics.g11-05

Cited by 8 publications

(14 citation statements)

References 25 publications

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“…Nonradiolabeled isomers of 1 and the following reference substances (Figure ) were used: 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl ( E / Z )-(1 R ,3 R )-3-formyl-2,2-dimethylcyclopropane-1-carboxylate ( 2 ), 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl ( E / Z )-(1 R ,3 R )-3-formyl-2,2-dimethylcyclopropane-1-carboxylic acid ( 3 ), [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methanol ( 4 ), (1 R ,3 R )-3-[( Z )-2-cyanoprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylic acid ( 5 -RTZ ), and (1 R ,3 R )-3-[( E )-2-cyanoprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylic acid ( 5 -RTE ). Eight isomers of 1 ( 1 - RCE , 1 - RCZ , 1 - RTE , 1 - RTZ , 1 - SCE , 1 - SCZ , 1 - STE , 1 - STZ ), 2 , 3 , and 4 were synthesized according to the reported methods. ,,− Compounds 5 -RTZ and 5 -RTE were obtained as follows: the corresponding isomer of 1 was hydrolyzed using 96% sulfonic acid for 30 min at ambient temperature followed by partition with tert -butylmethyl ether, and then the product was isolated using HPLC fractionation with method 1 described in the section titled Chromatography. Their chemical structures were confirmed by liquid chromatography–mass spectrometry (LC–MS) equipped with an electrospray ionization (ESI) interface and proton nuclear magnetic resonance ( 1 H NMR) analyses as follows.…”

Section: Methodsmentioning

confidence: 99%

Metabolism of the Pyrethroid Insecticide Momfluorothrin in Lettuce (Lactuca sativa L.)

Matsushima

Ando

Suzuki

et al. 2021

J. Agric. Food Chem.

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The metabolism of the insecticide momfluorothrin (1), 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (EZ)-(1R,3R)-3-(2-cyanoprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate, 14C-labeled at the benzyl or cyclopropyl carbon, was investigated in lettuce. The metabolic profiles were similar between the two active ingredients, 1-R-trans-Z and 1-R-trans-E. On the leaf surface, 1 gradually volatilized and penetrated into the plant with concomitant degradation to form aldehyde/carboxylic acid derivatives via oxidative cleavage of the propenyl double bond. No isomerization of 1 proceeded at any chiral carbon. In the leaf tissues, 1 underwent ester hydrolysis to give the corresponding alcohol and chrysanthemic acid moieties, followed by glucose conjugation and successive malonic acid or ribose modification. Assuming O3 or 1O2 as the major reactant for the degradation on the plant, the reactivity with the alkenyl group in the substructure methyl (1R,3R)-3-[(Z)-2-cyanoprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate was estimated from the HOMO/LUMO energy at the B3LYP/6-311+G** level, which indicated a lower potential of 1 than analogous pyrethroids due to its electron-withdrawing cyano group.

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Section: Methodsmentioning

confidence: 99%

Metabolism of the Pyrethroid Insecticide Momfluorothrin in Lettuce (Lactuca sativa L.)

Matsushima

Ando

Suzuki

et al. 2021

J. Agric. Food Chem.

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“…The major degradates detected were carbonaldehyde ( 4 ) and carboxylic acid ( 5 ) derivatives, which were decomposed from ozonide ( 2 ) and diol ( 6 ) produced by the activated oxygen species, that is, ozone and hydrogen peroxide, respectively. The photoisomerization hardly proceeded throughout the test duration . In the hydrolysis study, 1 - RTZ was moderately degraded by ester cleavage with a half-life of 26.8 days at pH 9 and 25 °C, whereas it was stable at pH 5 and 7.…”

Section: Introductionmentioning

confidence: 95%

“…The soil adsorption coefficient ( K oc ) of 1 - RTZ in three German soils was determined to be 3553–6142 mL g –1 oc by the batch equilibrium method . Under illumination on the moisture-controlled soil, 1 - RTZ degraded with a half-life of 8.1–12.0 days. , The photodegradation pathway was oxidation of the double bond at the prop-1-enyl moiety and cleavage of the ester linkage, followed by further decomposition to polar compounds and mineralization to carbon dioxide. The major degradates detected were carbonaldehyde ( 4 ) and carboxylic acid ( 5 ) derivatives, which were decomposed from ozonide ( 2 ) and diol ( 6 ) produced by the activated oxygen species, that is, ozone and hydrogen peroxide, respectively.…”

Section: Introductionmentioning

confidence: 99%

Metabolism of the Insecticide Metofluthrin in Cabbage (Brassica oleracea)

Ando

Fukushima

Fujisawa

et al. 2012

J. Agric. Food Chem.

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The metabolic fate of metofluthrin [2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (E,Z)-(1R,3R)-2,2-dimethyl-3-(prop-1-enyl)cyclopropanecarboxylate] separately labeled with (14)C at the carbonyl carbon and the α-position of the 4-methoxymethylbenzyl ring was studied in cabbage ( Brassica oleracea ). An acetonitrile solution of (14)C-metofluthrin at 431 g ai ha(-1) was once applied topically to cabbage leaves at head-forming stage, and the plants were grown for up to 14 days. Each isomer of metofluthrin applied onto the leaf surface rapidly volatilized into the air and was scarcely translocated to the untreated portion. On the leaf surface, metofluthrin was primarily degraded through ozonolysis of the propenyl side chain to produce the secondary ozonide, which further decomposed to the corresponding aldehyde and carboxylic acid derivatives. In the leaf tissues, the 1R-trans-Z isomer was mainly metabolized to its dihydrodiol derivative probably via an epoxy intermediate followed by saccharide conjugation in parallel with the ester cleavage, whereas no specific metabolite was dominant for the 1R-trans-E isomer. Isomerization of metofluthrin at the cyclopropyl ring was negligible for both isomers. In this study, the chemical structure of each secondary ozonide derivative was fully elucidated by the various modes of liquid chromatography-mass spectrometry (LC-MS) and nuclear magnetic resonance (NMR) spectroscopy together with cochromatography with the synthetic standard, and their cis/trans configuration was examined by the nuclear Overhauser effect (NOE) difference NMR spectrum.

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“…11,[15][16][17] The chemical purity of each metabolite was determined by HPLC to be greater than 98%. VII (99.4%) and IX (>97%) were purchased from Showa Denko K.K.…”

Section: Chemicalsmentioning

confidence: 99%

“…15) Furthermore, when I is distributed in the terrestrial environment, aerobic microbes in soil rapidly metabolize it via ester cleavage followed by successive oxidation 16) or it is photodegraded by sunlight on the soil surface. 17) Eight major metabolites (II-IX) detected through environmental fate studies, as shown in Fig. 1, have unique chemical structures different from other pyrethroids.…”

Section: Introductionmentioning

confidence: 99%

Acute aquatic toxicity of metofluthrin metabolites in the environment

et al. 2013

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Acute aquatic toxicity of eight major metabolites of the pyrethroid insecticide metofluthrin, potentially formed via oxidation and ester cleavage in the environment, was examined using three representative species, fathead minnow (Pimephales promelas), Daphnia magna and green alga (Pseudokirchneriella subcapitata). All metabolites showed a wide range of toxicity but were more than a hundredfold and tenfold less toxic than metofluthrin to pyrethroid-sensitive (fish and daphnid) and -insensitive (algal) taxa, respectively; 0.44 to >120 mg/L (fish 96-hr LC 50 ), 6.3 to >120 mg/L(daphnid 48-hr EC 50 ), and 2.6 to >110 mg/L (algal 96-hr E y C 50 ). The structural modification via ester cleavage and/or oxidation was found to significantly control the acute aquatic toxicity of the metabolites. The decreased lipophilicity in the metabolites generally resulted in much less acute toxicity, the extent of which was dependent on an introduced functional group such as formyl as a toxicophore and carboxyl causing a higher acidity.

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Photodegradation of insecticide metofluthrin on soil, clay minerals and glass surfaces

Cited by 8 publications

References 25 publications

Metabolism of the Pyrethroid Insecticide Momfluorothrin in Lettuce (Lactuca sativa L.)

Metabolism of the Pyrethroid Insecticide Momfluorothrin in Lettuce (Lactuca sativa L.)

Metabolism of the Insecticide Metofluthrin in Cabbage (Brassica oleracea)

Acute aquatic toxicity of metofluthrin metabolites in the environment

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