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Flumethrin

Flumethrin is a synthetic belonging to the class of alpha-cyano-3-phenoxyphenyl pyrethroids, with the molecular formula C₂₈H₂₂Cl₂FNO₃ and a molecular weight of 510.4 g/mol. It acts by prolonging the opening of sodium channels in nerve cells, disrupting normal nerve function in target parasites and leading to their paralysis and death. Primarily utilized in , flumethrin is applied externally to control ectoparasites such as ticks, fleas, biting and sucking lice, and s on including , sheep, , and , as well as on . It is formulated in various products, including 6% sprays or dips, 1% pour-ons for animals, and strips for treating varroatosis (a mite infestation) in honeybee hives. A notable application is in the Seresto® collar, where flumethrin is combined with to provide continuous protection against fleas, ticks, and chewing lice in and cats for up to eight months through slow release from the collar material; however, the collar has been subject to safety concerns, including reports of adverse effects in pets, and ongoing regulatory review by the EPA as of 2025. Flumethrin exhibits low in mammals, with oral LD₅₀ values ranging from 41 to 3800 mg/kg body weight and dermal LD₅₀ >2000 mg/kg in rats, though it can cause and eye upon contact. It is highly toxic to aquatic organisms and metabolized in the liver before via and in animals. The (ADI) for humans is set at 0–0.004 mg/kg body weight, reflecting its fat-soluble nature and potential for residue accumulation in animal products like and , for which maximum residue limits (MRLs) have been established.

Chemistry

Structure and properties

Flumethrin is classified as a Type II due to the presence of an α-cyano group on the moiety of its . The IUPAC name for flumethrin is (RS)-α-cyano-4-fluoro-3-phenoxybenzyl (1RS,3RS;1RS,3SR)-(EZ)-3-(β,4-dichlorostyryl)-2,2-dimethylcyclopropanecarboxylate, with the molecular formula C₂₈H₂₂Cl₂FNO₃ and a of 510.4 g/mol. As a chiral , flumethrin can exist in 16 possible stereoisomers arising from two chiral centers on the ring, the geometric isomerism (/) at the dichlorostyryl , and the chiral benzylic carbon. Commercial technical material is enriched in specific isomers, comprising more than 90% of the trans--1 and trans--2 forms (trans configuration at the ring and at the olefinic ), with less than 2% cis- and less than 1% trans- isomers. Flumethrin appears as a yellowish, highly viscous oil that is fat-soluble, with very low in (0.2 µg/L at 20°C in pure ) and high (log Kow = 6.2). The compound exhibits chemical stability under neutral conditions ( 4–7) but undergoes in alkaline environments, such as at 9.

Synthesis and production

Flumethrin is synthesized through a multi-step chemical process involving the construction of the ring via reactions and the preparation of halogenated aromatic intermediates, ultimately leading to esterification as the pivotal coupling step. The process begins with the of the acid component, trans-3-[2-chloro-2-(4-chlorophenyl)ethenyl]-2,2-dimethylcarboxylic acid, derived from appropriate vinyl precursors and addition to form the cyclopropane moiety. The alcohol counterpart is obtained from 4-fluoro-3-phenoxybenzaldehyde, which is converted to its derivative, 2-(4-fluoro-3-phenoxyphenyl)-2-hydroxyacetonitrile. The key esterification reaction couples the acid chloride of the cyclopropanecarboxylic acid with the alcohol under basic conditions, often with to stabilize the intermediate and promote toward the configuration. This reaction yields flumethrin as a of diastereoisomers, primarily the biologically active trans-Z-1 and trans-Z-2 forms. The is conducted in solvents to ensure high yield and control over impurity formation. Developed by AG in the and introduced commercially around under codes such as Bay VI 6045, the initial manufacturing process produced flumethrin with 30-45% trans-Z-1 and trans-Z-2 isomers, alongside 45-63% less active trans-E isomers and minor cis by-products. Subsequent refinements, including stereoselective and purification techniques, optimized the process to achieve over 90% trans-Z isomers in the current standard, with a typical ratio of approximately 55:45 (trans-Z-1 to trans-Z-2). continues to produce flumethrin, emphasizing these stereoselective methods to enhance efficacy while minimizing inactive stereoisomers. Technical-grade flumethrin exhibits a purity of 90-100%, with controlled impurities such as cis-Z isomers below 2% and trans-E isomers below 1%, ensuring compliance with regulatory standards for veterinary and apicultural applications. The production process includes rigorous purification stages, such as or , to meet these specifications.

Pharmacology

Mechanism of action

Flumethrin, a synthetic , primarily exerts its toxic effects by binding to voltage-gated sodium s in the membranes of target arthropods, thereby prolonging the open state of these channels during . This binding inhibits the phase of the action potential, leading to repetitive firing, hyperexcitation, , and eventual death of the or . The interaction occurs at a specific site on the , distinct from that of other insecticides like , and results in a use-dependent blockade that intensifies with repeated channel activation. As a Type II , flumethrin contains an alpha-cyano group in its molecular structure, which distinguishes it from Type I pyrethroids lacking this feature and enhances its binding affinity and duration of action on sodium channels. This structural modification allows for more potent and prolonged channel modification, producing a broader of neurotoxic symptoms compared to non-cyano pyrethroids, including increased disruption of impulse transmission. The alpha-cyano group contributes to slower dissociation from the , amplifying the insecticidal efficacy. Flumethrin operates predominantly through contact exposure, penetrating the of arthropods to reach tissues rapidly and inducing knockdown within minutes of application. This initial knockdown effect, characterized by immediate immobilization, progresses to lethal outcomes over several hours as the prolonged activity exhausts neural function. Its lipophilic nature, stemming from the carboxylic structure, facilitates this transcuticular absorption without requiring systemic uptake in the target organism. While the dominant mechanism involves disruption, flumethrin may also exert secondary effects by modulating gamma-aminobutyric acid ()-gated chloride channels and, to a lesser extent, nicotinic transmission in nerves, potentially contributing to enhanced neuroexcitation at higher doses. However, these interactions are subordinate to the primary effects and are not essential for its insecticidal activity. The higher potency of flumethrin in arthropods compared to mammals arises from species-specific differences in activity, particularly slower rates of and in , which allow the compound to persist longer at neural targets. In mammals, rapid hepatic via enzymes and hydrolysis reduces systemic exposure, conferring a wide margin. This metabolic disparity explains the compound's selectivity, with to being over 2000 times greater than to mammals.

Pharmacokinetics

Flumethrin, a highly lipophilic with a log P_ow of 6.2, exhibits distinct pharmacokinetic profiles in mammals and due to differences in and metabolic . Upon topical application, systemic in mammals is minimal, typically less than 2% of the applied dose penetrating the skin, as evidenced by studies in where approximately 71% of a 1.8 mg/kg body weight dose remained in the skin after 48 hours. In contrast, flumethrin demonstrates rapid dermal penetration in , facilitating quick contact toxicity characteristic of pyrethroids, which penetrate the efficiently to reach target sites. Following , flumethrin distributes preferentially to lipophilic compartments in mammals, accumulating in fatty tissues and remaining primarily at the site of application, such as or in treated like and sheep. In target parasites, high via direct contact enhances efficacy, whereas oral uptake in non-target mammals is limited by poor gastrointestinal and extensive first-pass . Metabolism in mammals occurs rapidly through ester hydrolysis mediated by carboxylesterases, cleaving the ester bond to form flumethrin , followed by cytochrome P450-mediated oxidation producing hydroxylated derivatives and further conjugation with or , resulting in non-toxic, water-soluble metabolites such as 4-fluoro-3-phenoxybenzoic . In , metabolic clearance is slower, contributing to prolonged exposure and enhanced compared to mammals. Excretion in mammals is primarily fecal (50-77% of the dose in and ruminants due to biliary secretion of lipophilic parent compound and metabolites), with urinary elimination of conjugated forms comprising the remainder; elimination is prolonged (e.g., 130-160 hours in rats following oral dosing), with slow release observed in . In , slower excretion prolongs residue persistence, aligning with the compound's extended activity against ectoparasites.

Applications

Veterinary uses

Flumethrin is widely used in veterinary medicine as a topical ectoparasiticide to control ticks (such as Ixodes and Rhipicephalus species), lice, and mites in livestock including cattle, sheep, goats, and horses. It is formulated as a 1% solution for pour-on application or a 6% solution for sprays and dips, with typical dosages ranging from 0.5 to 1 mg/kg body weight applied along the animal's backline. These external administration methods ensure targeted contact with ectoparasites while minimizing systemic absorption, as flumethrin's low solubility limits its need for internal distribution. In companion animals, flumethrin is incorporated into collars such as Seresto, which combines 4.5% flumethrin with 10% imidacloprid to provide sustained protection against fleas, ticks, and lice in dogs and cats for up to 8 months. As of 2025, the collar remains approved but is subject to ongoing safety evaluations by regulatory agencies due to reports of adverse events. The collar releases flumethrin at an initial rate of approximately 1 mg per day, gradually decreasing over time to maintain efficacy. In studies prior to widespread resistance, field trials demonstrated 94-100% efficacy in repelling and killing ticks on treated dogs, with rapid mortality (within 24 hours) and at least 90% reduction in tick counts persisting for 7-8 months; however, efficacy may be reduced in areas with pyrethroid-resistant tick populations. Pour-on formulations of flumethrin achieve 95-100% control in under field conditions in susceptible populations, with complete elimination of heavy infestations by day 4 post-treatment and a repellent effect that reduces host-seeking behavior by up to 90% in treated . Due to emerging and now widespread in populations to pyrethroids like flumethrin, veterinary guidelines recommend rotating with acaricides from different chemical classes to sustain long-term efficacy.

Apiculture

Flumethrin is widely used in apiculture for controlling the parasitic mite in honeybee (Apis mellifera) colonies, primarily through impregnated plastic strips such as Bayvarol. These strips contain 3.6 mg of flumethrin per strip and are placed between brood frames to allow bees to contact the active ingredient, which then spreads via bee activity to target phoretic mites on adult bees. However, to flumethrin has developed in many V. destructor populations worldwide, necessitating resistance monitoring and rotation with non-pyrethroid miticides. The standard application protocol involves using 4 strips per standard brood chamber (typically accommodating 10 frames), suspended by bending the tabs over the top edges of frames in the central brood area to ensure contact without impeding movement. Treatment duration is 6 weeks (42 days), after which strips must be removed; it is recommended during broodless or low-brood periods, such as late summer after harvest, to minimize exposure while maximizing efficacy against mites. Annual applications should be limited, ideally rotated with other miticides, to prevent resistance development in V. destructor populations. Early efficacy studies showed that flumethrin strips reduce Varroa infestation by 90-95% without causing significant disruption to brood development or colony health when applied correctly, but current efficacy varies due to , often requiring integrated . This high in susceptible populations stems from flumethrin's low , enabling sustained release over the treatment period, and its targeted primarily on phoretic mites rather than those in capped brood cells. Compared to more volatile alternatives, this approach provides reliable, long-lasting control with minimal residue risks in hive products when used per guidelines. Effective integration of flumethrin treatments requires ongoing monitoring of mite levels using non-destructive methods like the sugar roll test, where a sample of bees is dusted with powdered sugar to dislodge and count s, allowing beekeepers to assess thresholds (e.g., >3 s per 100 bees) and determine treatment timing.

Safety and toxicology

Toxicity to mammals

Flumethrin demonstrates low to mammals, with an oral LD50 of 41–3800 mg/kg body weight in rats, depending on the vehicle, classifying it as slightly to moderately toxic via this route. Dermal LD50 values are similarly high, greater than 2000 mg/kg in rats, reflecting limited absorption and minimal systemic effects at typical levels. However, it is a irritant (Category 2), potentially causing mild to moderate or upon direct contact, and it causes serious eye irritation (Category 2). Inhalation poses low risk, with an LC50 of approximately 225 mg/m³ in rats over 4 hours. Chronic exposure studies reveal no evidence of carcinogenicity, as long-term feeding trials in rats and mice showed no treatment-related tumor increases. Reproductive and developmental toxicity shows NOAELs of 1.7 mg/kg/day in rabbits and 0.5 mg/kg/day in rats, with no teratogenicity observed. Flumethrin undergoes rapid metabolism via mammalian esterases, preventing bioaccumulation and contributing to its favorable safety profile; this process, detailed in pharmacokinetic evaluations, results in quick elimination primarily through feces. In veterinary applications, it is well-tolerated in dogs from 7 weeks of age, with rare instances of transient local skin irritation at application sites, and reversible neurotoxic signs such as tremors or salivation only at doses exceeding therapeutic levels by 100-fold or more. Despite general tolerance, the Seresto collar has been associated with thousands of reported pet injuries and deaths (as of 2024), prompting EPA warnings and ongoing reviews for potential neurotoxicity or skin reactions. Cats exhibit greater sensitivity to pyrethroids like flumethrin compared to dogs, necessitating lower dosing to avoid similar neurotoxic effects. For humans, particularly veterinary handlers, risks are primarily dermal or inhalational, manifesting as or mild respiratory irritation; no systemic poisonings have been reported from approved uses. (PPE), such as gloves and masks, is recommended during application to mitigate these effects, with margin of exposure () values exceeding 100 for typical handler scenarios, underscoring low overall risk. The compound's selectivity stems from its 100- to 2250-fold lower potency in mammals versus , attributable to efficient enzymes.

Toxicity to non-target organisms

Flumethrin exhibits high acute toxicity to fish, with a 96-hour LC50 of 0.17 mg/L reported for rainbow trout (Oncorhynchus mykiss). This toxicity is attributed to the compound's rapid absorption through fish gills and slow metabolic degradation in aquatic species, leading to neurotoxic effects that disrupt sodium channel function. Similarly, aquatic invertebrates are highly sensitive, as evidenced by a 48-hour EC50 of 0.0027 mg/L for Daphnia magna. In honey bees (Apis mellifera), flumethrin demonstrates high acute oral , with a 48-hour LD50 of 0.178 µg per bee. Sublethal larval exposure to residues, such as those occurring in hive materials at concentrations of 0.03–0.13 mg/kg in , impairs development by downregulating genes involved in and protein synthesis, resulting in increased mortality, delayed pupation, and reduced emergence rates. For instance, exposure at 0.1–1 mg/L during the larval stage significantly lowers survival and induces long-term behavioral alterations in adults, including precocious and deficits. Pour-on applications of flumethrin in lead to residues in that can affect dung beetles, though impacts vary by and timing. In Euoniticellus intermedius, remains unaffected, but is reduced around 7 days post-treatment, with fewer brood balls produced (approximately 43% fewer than controls), potentially limiting in contaminated pastures. Flumethrin poses low direct oral toxicity to , consistent with profiles where LD50 values exceed 2000 mg/kg body weight. However, secondary poisoning risks exist for , particularly raptors or consuming contaminated prey from treated , though specific cases for flumethrin are limited compared to other pesticides. Resistance in Varroa destructor mites to flumethrin, often involving mutations in the voltage-gated sodium channel and cross-resistance to other pyrethroids like tau-fluvalinate, complicates control efforts and may indirectly heighten exposure risks to non-target bees through prolonged acaricide use.

Environmental effects

Persistence and fate

Flumethrin demonstrates moderate persistence in soil under aerobic conditions, with a degradation half-life (DT50) of 90 days. In environments, flumethrin's low of 9.7 × 10⁻⁵ mg/L at 20°C severely limits its mobility and potential for . The compound strongly adsorbs to and sediments, with estimated soil organic carbon-water partition coefficients (Koc) exceeding 10,000 for similar pyrethroids, indicating negligible contamination risk. Within and dung from treated , flumethrin residues persist up to 28 days post-application, with limited impacts on dung by certain . Atmospheric degradation of flumethrin is rapid, with a of less than 1 day due to reaction with hydroxyl radicals. Bioaccumulation potential is low, attributed to efficient and in organisms.

Ecological impacts

Flumethrin, a synthetic used primarily in veterinary ectoparasite control, enters ecosystems mainly through from treated and overspray during application, leading to contamination. This exposure is highly toxic to invertebrates, with concentrations as low as 1 μg/L causing behavioral alterations, growth inhibition, and reproductive impairment, while levels exceeding 10 μg/L can result in direct mortality among sensitive species such as microcrustaceans and . Such impacts cascade through food webs by eliminating key primary consumers like microzooplankton, thereby reducing prey availability for higher trophic levels including and amphibians, and altering overall community structure. In terrestrial environments, flumethrin applications to via pour-on formulations result in minimal residues in dung, leading to limited direct effects on populations compared to other pyrethroids. Studies on like Euoniticellus intermedius have shown no significant reduction in , , or dung colonization following exposure to dung from flumethrin-treated , preserving essential services such as soil aeration and nutrient recycling. However, broader concerns persist for soil-dwelling in areas with high application rates, where potential accumulation could indirectly affect microbial communities and . Sublethal exposure to flumethrin poses risks to pollinators, particularly honey bees (Apis mellifera), which encounter residues during mite control or environmental contamination. Larval exposure to sublethal doses impairs , pupation, and adult emergence rates, while adult bees experience shortened lifespan, weakened immunity, and disrupted foraging behavior, including reduced flight efficiency and orientation. These effects compromise hive hygiene and overall health, exacerbating stress from other factors despite flumethrin's targeted benefits against parasites. As of 2025, ongoing studies highlight increased in mites, potentially leading to higher usage and amplified ecological risks. Overreliance on flumethrin in pest management contributes to development in target organisms like the (Varroa destructor) and ticks, necessitating higher application rates or rotations that intensify selective pressure and disrupt (IPM) strategies. , often linked to mutations in voltage-gated sodium channels, has been documented in various regions, leading to treatment failures and increased reliance on alternative acaricides, which can amplify ecological pressures through broader chemical use. Effective IPM approaches emphasize rotation with non-pyrethroid options and monitoring to delay onset. Mitigation measures, such as establishing vegetative filter strips (VFS) of at least 10-30 meters around water bodies and timing applications to avoid rainfall, can reduce runoff and spray drift of flumethrin by 50% or more, minimizing off-site transport to aquatic and terrestrial habitats. These practices, combined with precision application techniques like targeted pour-ons, help preserve while maintaining efficacy against pests.

History and regulation

Development

Flumethrin was developed by AG in the as part of broader advancements in synthetic pyrethroids designed for veterinary applications, initially under the developmental code BAY VI6045. The compound's emphasized enhanced photostability and persistence relative to natural pyrethrins, addressing limitations in earlier insecticides. First patents covering flumethrin were granted in 1978. Early field trials in 1979 confirmed its high efficacy against cattle ticks (Boophilus spp.), paving the way for the commercial launch of the Bayticol pour-on formulation in 1981 as a topical ectoparasiticide for . Subsequent refinements in manufacturing optimized the isomeric composition, increasing the trans-isomer content from initial mixtures of 30-45% to over 90% (primarily trans-Z-1 and trans-Z-2 diastereomers in a of approximately :45), which improved potency and biological activity. By 1985, flumethrin's applications expanded to apiculture through the introduction of Bayvarol plastic strips impregnated with the active ingredient (3.6 mg per strip), targeting mites in bee colonies. A significant regulatory milestone came in 1996 with the first evaluation by the Joint FAO/WHO Meeting on Pesticide Residues (JMPR), which reviewed , residue levels in animal products and , and established an of 0-0.004 mg/kg body weight while recommending maximum residue limits for commodities like cattle fat (0.2 mg/kg) and (0.05 mg/kg).

Regulatory status

Flumethrin is registered by the (EPA) for veterinary use as an ectoparasiticide on and companion animals, with the first registration occurring in 2012 for the technical grade active ingredient and associated end-use products such as tick . Residential applications, such as in home gardens or non-veterinary settings, are not permitted, limiting its use to targeted animal treatments to minimize human exposure risks. The EPA has established maximum residue limits (MRLs) for flumethrin in animal-derived foods, including 0.05 mg/kg in cattle milk and 0.2 mg/kg in fat tissues of ruminants, to ensure while accommodating external veterinary applications. In 2023, the EPA extended the registration of the Seresto amid reports of adverse incidents, requiring enhanced warnings for . In the , flumethrin is authorized as a veterinary medicinal product for ectoparasite control under relevant frameworks, including evaluations for residue levels in food-producing animals. A 2016 review by the (EFSA) analyzed residues, including flumethrin, in food samples across member states, confirming overall low occurrence but emphasizing the need for protective measures against aquatic contamination due to its persistence in sediments. Use is restricted on lactating animals intended for production to prevent residues in products, aligning with EU standards. It is recommended for use in for ectoparasites, with emphasis on protective equipment for applicators. Restrictions on flumethrin include bans on its formulation in sheep dip products in the , where all synthetic pyrethroid-based dips were permanently withdrawn from the market in 2006 due to environmental persistence and concerns in water bodies. Resistance monitoring is mandated in regions with ongoing use, such as operations, to track efficacy against target parasites like ticks and mites. Recent reassessments in and have focused on apicultural applications, with Canada's Pest Management Regulatory Agency confirming in a 2016 re-evaluation (updated through ongoing monitoring) that flumethrin strips for mite control pose low risk to bees when used as directed, requiring bee-safe labeling to prevent overuse. In , the Australian Pesticides and Veterinary Medicines Authority initiated a chemical review of flumethrin in 2023, which was completed as of 2025, emphasizing updated labeling for bee safety and environmental protections in veterinary products.