11/02/2023, 16:06 Pyrethroid - Wikipedia
Pyrethroid
A pyrethroid is an organic compound similar to the natural pyrethrins, which are produced by
the flowers of pyrethrums (Chrysanthemum cinerariaefolium and C. coccineum). Pyrethroids are
used as commercial and household insecticides.[1]
Chemical structure of Allethrin isomers
Chemical structure of Permethrin isomers
In household concentrations pyrethroids are generally harmless to humans.[1] However,
pyrethroids are toxic to insects such as bees, dragonflies, mayflies, gadflies, and some other
invertebrates, including those that constitute the base of aquatic and terrestrial food webs.[2]
Pyrethroids are toxic to aquatic organisms, especially fish.[3] They have been shown to be an
effective control measure for malaria outbreaks, through indoor applications.[4]
Mode of action
Pyrethroids are axonic excitotoxins, the toxic effects of which are mediated through preventing
the closure of the voltage-gated sodium channels in the axonal membranes. The sodium channel
is a membrane protein with a hydrophilic interior. This interior is shaped precisely to allow
sodium ions to pass through the membrane, enter the axon, and propagate an action potential.
When the toxin keeps the channels in their open state, the nerves cannot repolarize, leaving the
axonal membrane permanently depolarized, thereby paralyzing the organism.[5] Pyrethroids can
be combined with the synergist piperonyl butoxide, a known inhibitor of microsomal cytochrome
P450 enzymes which are important in metabolizing the pyrethroid. By that means, the efficacy
(lethality) of the pyrethroid is increased.[6] It is likely that there are other mechanisms of
intoxication also.[7] Disruption of neuroendocrine activity is thought to contribute to their
irreversible effects on insects, which indicates a pyrethroid action on voltage-gated calcium
channels (and perhaps other voltage-gated channels more widely).[7]
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Chemistry and classification
(1R,3R)- or (+)-trans-chrysanthemic
acid.
Pyrethroids are classified based on their mechanism of biological action, as they do not share a
common chemical structure. Many are 2,2-dimethylcyclopropanecarboxylic acid derivatives, like
chrysanthemic acid, esterified with an alcohol. However, the cyclopropyl ring does not occur in
all pyrethroids. Fenvalerate, which was developed in 1972, is one such example and was the first
commercialized pyrethroid without that group.
Pyrethroids which lack an α-cyano group are often classified as type I pyrethroids and those with
it are called type II pyrethroids. Pyrethroids that have a common name starting with "cy" have a
cyano group and are type II. Fenvalerate also contains an α-cyano group.
Some pyrethroids, like etofenprox, also lack the ester bond found in most other pyrethroids and
have an ether bond in its place. Silafluofen is also classified as a pyrethroid and has a silicon
atom in the place of the ester. Pyrethroids often have chiral centers and only certain
stereoisomers work efficiently as insecticides.[8]
Examples
Allethrin, the first pyrethroid synthesized
Bifenthrin, active ingredient of Talstar, Capture, Ortho Home Defense Max, and Bifenthrine
Cyfluthrin, an active ingredient in Baygon, Temprid, Fumakilla Vape Aerosol, Tempo SC, and
many more, dichlorovinyl derivative of pyrethrin
Cypermethrin, including the resolved isomer alpha-cypermethrin, dichlorovinyl derivative of
pyrethrin. Commonly found in crawling insect killers and some mosquito sprays.
Cyphenothrin, active ingredient of K2000 Insect spray sold in Israel. Mostly used in some
aerosols as a Cypermethrin substitute in developing countries.
Deltamethrin, dibromovinyl derivative of pyrethrin
Dimefluthrin
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Esfenvalerate
Etofenprox
Fenpropathrin
Fenvalerate
Flucythrinate
Flumethrin
Imiprothrin
lambda-Cyhalothrin
Metofluthrin
Permethrin, dichlorovinyl derivative of pyrethrin and most widely used pyrethroid.
Phenothrin (Sumithrin), active ingredient of Anvil
Prallethrin
Resmethrin, active ingredient of Scourge
Silafluofen
tau-Fluvalinate
Tefluthrin
Tetramethrin
Tralomethrin
Transfluthrin, an active ingredient in Baygon and other products.
Environmental effects
Pyrethroids are toxic to insects such as bees, dragonflies, mayflies, gadflies, and some other
invertebrates, including those that constitute the base of aquatic and terrestrial food webs.[2]
They are toxic to aquatic organisms including fish.[3]
Biodegradation
Pyrethroids are usually broken apart by sunlight and the atmosphere in one or two days,
however when associated with sediment they can persist for some time.[9]
Pyrethroids are unaffected by conventional secondary treatment systems at municipal
wastewater treatment facilities. They appear in the effluent, usually at levels lethal to
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invertebrates.[10]
Safety
Humans
Pyrethroid absorption can happen via skin, inhalation or ingestion.[11] Pyrethroids often do not
bind efficiently to mammalian sodium channels.[12] They also absorb poorly via skin and human
liver is often able to metabolize them relatively efficiently. Pyrethroids are thus much less toxic to
humans than to insects.[13]
It is not well established if chronic exposure to small amounts of pyrethroids is hazardous or
not.[14] However, large doses can cause acute poisoning, which is rarely life threatening. Typical
symptoms include facial paresthesia, itching, burning, dizziness, nausea, vomiting and more
severe cases of muscle twitching. Severe poisoning is often caused by ingestion of pyrethroids
and can result in a variety of symptoms like seizures, coma, bleeding or pulmonary edema.[11]
There is an association of pyrethroids with poorer early social-emotional and language
development.[4]
Other organisms
Pyrethroids are very toxic to cats, but not to dogs. Poisoning in cats can result in seizures, fever,
ataxia and even death. Poisoning can occur if pyrethroid containing flea treatment products,
which are intended for dogs, are used on cats. The livers of cats detoxify pyrethroids via
glucuronidation more poorly than dogs, which is the cause of this difference.[15] Aside from cats,
pyrethroids are typically not toxic to mammals or birds.[16] They are often toxic to fish, reptiles
and amphibians.[17]
Resistance
The use of pyrethroids as insecticides has led to the development of widespread resistance to
them among some insect populations, especially mosquitoes.[18] Although bedbugs were almost
eradicated in North America through the use of DDT and organophosphates, populations of
bedbugs resistant to both have developed. The use of DDT for this purpose was banned, and its
reintroduction would not offer a solution to the problem of bedbugs, due to resistance.[19]
Pyrethroids became more commonly used against bedbugs, but resistant populations have now
developed to them as well.[20][21][22][23] Populations of Diamondback moths have also commonly
developed resistance to pyrethroids[24] – including in U.S. states North Dakota[25] and
Wisconsin[26] while pyrethroids are still recommended in California.[27] Various mosquito
populations have been discovered to have a high level of resistance, including Anopheles
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gambiae s.l. in West Africa by Chandre et al 1999 through Pwalia et al 2019, A. arabiensis in
Sudan by Ismail et al 2018 and The Gambia by Opondo et al 2019, and Aedes aegypti in South
East Asia by Amelia-Yap et al 2018, Papua New Guinea by Demok et al 2019, and various other
locations by Smith et al 2016.[18]
History
Pyrethroids were introduced by a team of Rothamsted Research scientists in the 1960s and 1970s
following the elucidation of the structures of pyrethrin I and II by Hermann Staudinger and
Leopold Ružička in the 1920s.[28] The pyrethroids represented a major advancement in the
chemistry that would synthesize the analog of the natural version found in pyrethrum. Its
insecticidal activity has relatively low mammalian toxicity and an unusually fast biodegradation.
Their development coincided with the identification of problems with DDT use. Their work
consisted firstly of identifying the most active components of pyrethrum, extracted from East
African chrysanthemum flowers and long known to have insecticidal properties. Pyrethrum
rapidly knocks down flying insects but has negligible persistence — which is good for the
environment but gives poor efficacy when applied in the field. Pyrethroids are essentially
chemically stabilized forms of natural pyrethrum and belong to IRAC MoA group 3 (they interfere
with sodium transport in insect nerve cells).[29]
The first-generation pyrethroids, developed in the 1960s, include bioallethrin, tetramethrin,
resmethrin, and bioresmethrin. They are more active than the natural pyrethrum but are unstable
in sunlight. With the 91/414/EEC review,[30] many 1st-generation compounds have not been
included on Annex 1, probably because the market is not big enough to warrant the costs of re-
registration (rather than any special concerns about safety).
By 1974, the Rothamsted team had discovered a second generation of more persistent
compounds notably: permethrin, cypermethrin and deltamethrin. They are substantially more
resistant to degradation by light and air, thus making them suitable for use in agriculture, but
they have significantly higher mammalian toxicities. Over the subsequent decades these
derivatives were followed with other proprietary compounds such as fenvalerate, lambda-
cyhalothrin and beta-cyfluthrin. Most patents have now expired, making these compounds cheap
and therefore popular (although permethrin and fenvalerate have not been re-registered under
the 91/414/EEC process).
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