Flupyradifurone

Last updated
Flupyradifurone
Flupyradifuron.svg
Names
IUPAC name
4-[(6-Chloropyridine-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-one
Other names
Flupyradifurone, Sivanto
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.231.094 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 804-373-8
PubChem CID
UNII
  • InChI=1S/C12H11ClF2N2O2/c13-10-2-1-8(4-16-10)5-17(6-11(14)15)9-3-12(18)19-7-9/h1-4,11H,5-7H2
    Key: QOIYTRGFOFZNKF-UHFFFAOYSA-N
  • C1C(=CC(=O)O1)N(CC2=CN=C(C=C2)Cl)CC(F)F
Properties
C12H11ClF2N2O2
Molar mass 288.68 g·mol−1
AppearanceWhite to beige solid
Odor None
Density 1.43 g/mL
Melting point 69 °C (156 °F; 342 K)
3.2 g/L (pH 4)

3.0 g/L (pH 7)

Solubility in Other0.0005 g/L (n-Heptane)

>250 g/L (Methanol)

Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Warning
H302, H373, H410
P260, P264, P270, P273, P301+P312, P314, P330, P391, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Flupyradifurone is a systemic butenolide insecticide developed by Bayer CropScience under the name Sivanto. Flupyradifurone protects crops from sap-feeding pests such as aphids and is safer for non-target organisms compared to other insecticides. [1] Sivanto was launched in 2014 since it obtained its first commercial registration in central America (Guatemala and Honduras). [2] Insecticide Resistance Action Committee (IRAC) classified Flupyradifurone as 4D subset (butenolide) and it is the first pesticide in the butenolide category. [3] [4] It was approved by European Union in 2015. [5]

Contents

Characteristics

Aphid Aphid on leaf05.jpg
Aphid

Sap-feeding insects have developed resistance to nearly all other kinds of insecticides [6] but flupyradifurone is effective at controlling aphids and whitefly, thereby maintaining yields of crops such as vegetables, fruits, cotton, and coffee. [7] It also demonstrated positive toxicological and ecotoxicological safety. [2]

According to a study by Bayer, who developed the compound, flupyradifurone has a high rate of uptake by plants and crops. The authors used phosphor imaging analysis to monitor the uptake and translocation of [pyridinylmethyl-14C]-labeled flupyradifurone by tomato plants. [2] The result revealed fast root uptake and the even distribution of labeled flupyradifurone in the entire plant. Flupyradifurone is delivered via xylem translocation in the plants. The concentration in the plants reached the highest point in 7 and 14 days. After 24 days of the application, a significant decline is observed. [2] Flupyradifurone also featured excellent speed of action. The speed of action can be observed by the prohibition of honeydew excretion. After applying the flupyradifurone to the plant by spraying, the honeydew excretion is inhibited within 2 hours and all the aphids die after 48 hours. The result demonstrated that flupyradifurone has an exceptional speed of action compared to other insecticides. [2]

Flupyradifurone presented potent efficacy in controlling aphids and whiteflies. According to bioassays research, the flupyradifurone has lower LC50 numbers of aphid and whitefly compared to imidacloprid. [2] In the field trial, flupyradifurone controlled the lettuce aphid at a favorable rate via foliar applying. It had the highest efficiency (96%) of controlling lettuce aphid after 6–10 days of the application. [2]

Mode of action

Flupyradifurone is an agonist of insect nicotinic acetylcholine receptors, [8] [2] causing depolarization of nerve cells membranes. [7] Insects cannot detoxify flupyradifurone according to the research of CYP6CM1-mediated metabolism. [2] Since flupyradifurone cannot be inactivated by acetylcholinesterase, it will lead to the failure of nerve system of insects and end up with the death of insects. [7]

Synthesis

Flupyradifurone is structurally related to the natural insecticide, stemofoline which occurs in the plant species Stemona japonica . [9] [2] Stemofoline has some advantageous features, such as being fast-acting and an effective antifeedant, but does not efficiently bind to insect nicotinic acetylcholine receptors. [10] [11]

There are two ways to synthesis flupyradifurone. First, flupyradifurone can be synthesized from reacting tetronic acid with 2,2-difluoroethylamine to produce the intermediate, 4-[(2-fluoroethyl)amino]furane-2(5H)-one. Heating the reaction intermediate with 2-chloro-5-(chloromethyl)pyridine in THF under reflux yields flupyradifurone. [2] In the second method, tetronic acid, 4-touluenesulfonic acid, and N-[(6-chloropyridin-3-yl)methyl]-2,2-difluoroethane-1-amine in toluene are heated under reflux for 2 hours to produce flupyradifurone. [2]

Toxicological and ecotoxicological safety

Using the U.S. Environmental Protection Agency guidelines to classify carcinogenic effects, flupyradifurone is categorized as "not likely to be carcinogenic to humans." It is not irritant to humans' eyes and skin, [2] [12] and the EPA is not concerned about occupational exposure. [12]

For the non-target species, flupyradifurone also presents toxicological safety at low concentration. [12] [ disputed (for: ref states "Aquatic Life Exposure – Flupyradifurone is very highly toxic to aquatic and benthic invertebrates." and that it is mobile from treated fields into groundwater) ] Flupyradifurone will still bind to the nicotinic acetylcholine receptors of honey bees, however, it will only affect the taste and appetitive learning performance at the highest labeled concentration. [13] The LD50 of honey bee acute contact is >100 μg/bee and acute oral is 1200 ng/bee. For bumblebee, the acute contact LD50 is >100 μg/bee.

Related Research Articles

<span class="mw-page-title-main">Insecticide</span> Pesticide used against insects

Insecticides are pesticides used to kill insects. They include ovicides and larvicides used against insect eggs and larvae, respectively. Insecticides are used in agriculture, medicine, industry and by consumers. Insecticides are claimed to be a major factor behind the increase in the 20th-century's agricultural productivity. Nearly all insecticides have the potential to significantly alter ecosystems; many are toxic to humans and/or animals; some become concentrated as they spread along the food chain.

<span class="mw-page-title-main">Pesticide resistance</span> Decreased effectiveness of a pesticide on a pest

Pesticide resistance describes the decreased susceptibility of a pest population to a pesticide that was previously effective at controlling the pest. Pest species evolve pesticide resistance via natural selection: the most resistant specimens survive and pass on their acquired heritable changes traits to their offspring. If a pest has resistance then that will reduce the pesticide's efficacy – efficacy and resistance are inversely related.

<span class="mw-page-title-main">Imidacloprid</span> Chemical compound

Imidacloprid is a systemic insecticide belonging to a class of chemicals called the neonicotinoids which act on the central nervous system of insects. The chemical works by interfering with the transmission of stimuli in the insect nervous system. Specifically, it causes a blockage of the nicotinergic neuronal pathway. By blocking nicotinic acetylcholine receptors, imidacloprid prevents acetylcholine from transmitting impulses between nerves, resulting in the insect's paralysis and eventual death. It is effective on contact and via stomach action. Because imidacloprid binds much more strongly to insect neuron receptors than to mammal neuron receptors, this insecticide is more toxic to insects than to mammals.

<span class="mw-page-title-main">Chlorfenvinphos</span> Chemical compound

Chlorfenvinphos is an organophosphorus compound that was widely used as an insecticide and an acaricide. The molecule itself can be described as an enol ester derived from dichloroacetophenone and diethylphosphonic acid. Chlorfenvinphos has been included in many products since its first use in 1963. However, because of its toxic effect as a cholinesterase inhibitor it has been banned in several countries, including the United States and the European Union. Its use in the United States was cancelled in 1991.

Pesticides vary in their effects on bees. Contact pesticides are usually sprayed on plants and can kill bees when they crawl over sprayed surfaces of plants or other areas around it. Systemic pesticides, on the other hand, are usually incorporated into the soil or onto seeds and move up into the stem, leaves, nectar, and pollen of plants.

<span class="mw-page-title-main">Sooty mold</span> Name for several species of fungus

Sooty mold is a collective term for different Ascomycete fungi, which includes many genera, commonly Cladosporium and Alternaria. It grows on plants and their fruit, but also environmental objects, like fences, garden furniture, stones, and even cars. The mold benefits from either a sugary exudate produced by the plant or fruit, or honeydew-secreting insects or sap suckers the plant may be infested by.

<i>Stemona</i> Genus of vines

Stemona is a genus of vines and subshrubs in the family Stemonaceae, described as a genus in 1790.

Neonicotinoids are a class of neuro-active insecticides chemically similar to nicotine, developed by scientists at Shell and Bayer in the 1980s.

<span class="mw-page-title-main">Spinosad</span> Medication

Spinosad is an insecticide based on chemical compounds found in the bacterial species Saccharopolyspora spinosa. The genus Saccharopolyspora was discovered in 1985 in isolates from crushed sugarcane. The bacteria produce yellowish-pink aerial hyphae, with bead-like chains of spores enclosed in a characteristic hairy sheath. This genus is defined as aerobic, Gram-positive, nonacid-fast actinomycetes with fragmenting substrate mycelium. S. spinosa was isolated from soil collected inside a nonoperational sugar mill rum still in the Virgin Islands. Spinosad is a mixture of chemical compounds in the spinosyn family that has a generalized structure consisting of a unique tetracyclic ring system attached to an amino sugar (D-forosamine) and a neutral sugar (tri-Ο-methyl-L-rhamnose). Spinosad is relatively nonpolar and not easily dissolved in water.

<span class="mw-page-title-main">Nitenpyram</span> Insecticide

Nitenpyram is a chemical frequently used as an insecticide in agriculture and veterinary medicine. The compound is an insect neurotoxin belonging to the class of neonicotinoids which works by blocking neural signaling of the central nervous system. It does so by binding irreversibly to the nicotinic acetylcholine receptor (nACHr) causing a stop of the flow of ions in the postsynaptic membrane of neurons leading to paralysis and death. Nitenpyram is highly selective towards the variation of the nACHr which insects possess, and has seen extensive use in targeted, insecticide applications.

<span class="mw-page-title-main">Clothianidin</span> Chemical compound

Clothianidin is an insecticide developed by Takeda Chemical Industries and Bayer AG. Similar to thiamethoxam and imidacloprid, it is a neonicotinoid. Neonicotinoids are a class of insecticides that are chemically similar to nicotine, which has been used as a pesticide since the late 1700s. Clothianidin and other neonicotinoids act on the central nervous system of insects as an agonist of nAChR, the same receptor as acetylcholine, the neurotransmitter that stimulates and activating post-synaptic acetylcholine receptors but not inhibiting AChE. Clothianidin and other neonicotinoids were developed to last longer than nicotine, which is more toxic and which breaks down too quickly in the environment.

<i>Myzus persicae</i> Aphid of peach, potato, other crops

Myzus persicae, known as the green peach aphid, greenfly, or the peach-potato aphid, is a small green aphid belonging to the order Hemiptera. It is the most significant aphid pest of peach trees, causing decreased growth, shrivelling of the leaves and the death of various tissues. It also acts as a vector for the transport of plant viruses such as cucumber mosaic virus (CMV), potato virus Y (PVY) and tobacco etch virus (TEV). Potato virus Y and potato leafroll virus can be passed to members of the nightshade/potato family (Solanaceae), and various mosaic viruses to many other food crops.

<i>Tuta absoluta</i> Pest worm of tomato, potato, and others

Tuta absoluta or Phthorimaea absoluta is a species of moth in family Gelechiidae known by the common names South American tomato pinworm, tomato leafminer, tomato pinworm and South American tomato moth. It is well known as a serious pest of tomato crops in Europe, Africa, western Asia and South and Central America, with larvae causing up to 100% loss if not effectively controlled.

<span class="mw-page-title-main">Acetamiprid</span> Chemical compound

Acetamiprid is an organic compound with the chemical formula C10H11ClN4. It is an odorless neonicotinoid insecticide produced under the trade names Assail, and Chipco by Aventis CropSciences. It is systemic and intended to control sucking insects (Thysanoptera, Hemiptera, mainly aphids) on crops such as leafy vegetables, citrus fruits, pome fruits, grapes, cotton, cole crops, and ornamental plants. It is also a key pesticide in commercial cherry farming due to its effectiveness against the larvae of the cherry fruit fly.

<span class="mw-page-title-main">Thiamethoxam</span> Chemical compound

Thiamethoxam is the ISO common name for a mixture of cis-trans isomers used as a systemic insecticide of the neonicotinoid class. It has a broad spectrum of activity against many types of insects and can be used as a seed dressing.

<span class="mw-page-title-main">Dinotefuran</span> Chemical compound

Dinotefuran is an insecticide of the neonicotinoid class developed by Mitsui Chemicals for control of insect pests such as aphids, whiteflies, thrips, leafhoppers, leafminers, sawflies, mole cricket, white grubs, lacebugs, billbugs, beetles, mealybugs, and cockroaches on leafy vegetables, in residential and commercial buildings, and for professional turf management. Its mechanism of action involves disruption of the insect's nervous system by inhibiting nicotinic acetylcholine receptors. In order to avoid harming beneficial insects such as bees, it should not be applied during bloom.

<span class="mw-page-title-main">Thiacloprid</span> Chemical compound

Thiacloprid is an insecticide of the neonicotinoid class. Its mechanism of action is similar to other neonicotinoids and involves disruption of the insect's nervous system by stimulating nicotinic acetylcholine receptors. Thiacloprid was developed by Bayer CropScience for use on agricultural crops to control of a variety of sucking and chewing insects, primarily aphids and whiteflies.

<span class="mw-page-title-main">Sulfoxaflor</span> Chemical compound

Sulfoxaflor, also marketed as Isoclast, is a systemic insecticide that acts as an insect neurotoxin. A pyridine and a trifluoromethyl compound, it is a member of a class of chemicals called sulfoximines, which act on the central nervous system of insects.

The Insecticide Resistance Action Committee (IRAC) was formed in 1984 and works as a specialist technical group of the industry association CropLife to be able to provide a coordinated industry response to prevent or delay the development of insecticide resistance in insect and mite pests. IRAC strives to facilitate communication and education on insecticide and traits resistance as well as to promote the development and facilitate the implementation of insecticide resistance management strategies.

<span class="mw-page-title-main">Nereistoxin</span> Chemical compound

Nereistoxin is a natural product identified in 1962 as the toxic organic compound N,N-dimethyl-1,2-dithiolan-4-amine. It had first been isolated in 1934 from the marine annelid Lumbriconereis heteropoda and acts by blocking the nicotinic acetylcholine receptor. Researchers at Takeda in Japan investigated it as a possible insecticide. They subsequently developed a number of derivatives that were commercialised, including those with the ISO common names bensultap, cartap, thiocyclam and thiosultap.

References

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  2. 1 2 3 4 5 6 7 8 9 10 11 12 13 Nauen, Ralf; Jeschke, Peter; Velten, Robert; Beck, Michael E.; Ebbinghaus-Kintscher, Ulrich; Thielert, Wolfgang; Wölfel, Katharina; Haas, Matthias; Kunz, Klaus; Raupach, Georg (2015). "Flupyradifurone: a brief profile of a new butenolide insecticide". Pest Management Science. 71 (6): 850–862. doi:10.1002/ps.3932. ISSN   1526-4998. PMC   4657471 . PMID   25351824.
  3. "Interactive MoA Classification | Insecticide Resistance Action Committee (IRAC)". IRAC. Retrieved 2021-11-30.
  4. "Regulations.gov". www.regulations.gov. Retrieved 2021-11-30.
  5. Commission Implementing Regulation (EU) 2015/2084 of 18 November 2015 approving the active substance flupyradifurone, in accordance with Regulation (EC) No 1107/2009 of the European Parliament and of the Council concerning the placing of plant protection products on the market, and amending the Annex to Commission Implementing Regulation (EU) No 540/2011 (Text with EEA relevance), 2015-11-19, retrieved 2021-12-01
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  8. "Flupyradifurone: A new insecticide or just another neonicotinoid?". Pesticide Research Institute. 2015-02-05. Retrieved 2021-11-30.
  9. Yamamoto, Izuru; Casida, John E., eds. (1999). Nicotinoid Insecticides and the Nicotinic Acetylcholine Receptor. p. 46. doi:10.1007/978-4-431-67933-2. ISBN   978-4-431-68011-6. S2CID   34374399.
  10. Kaltenegger, Elisabeth; Brem, Brigitte; Mereiter, Kurt; Kalchhauser, Hermann; Kählig, Hanspeter; Hofer, Otmar; Vajrodaya, Srumya; Greger, Harald (August 2003). "Insecticidal pyrido[1,2-a]azepine alkaloids and related derivatives from Stemona species". Phytochemistry. 63 (7): 803–816. doi:10.1016/s0031-9422(03)00332-7. ISSN   0031-9422. PMID   12877922.
  11. Mungkornasawakul, Pitchaya; Pyne, Stephen G.; Jatisatienr, Araya; Supyen, Damrat; Jatisatienr, Chaiwat; Lie, Wilford; Ung, Alison T.; Skelton, Brian W.; White, Allan H. (2004-03-02). "Phytochemical and Larvicidal Studies on Stemona curtisii: Structure of a New Pyrido[1,2-a]azepine Stemona Alkaloid". Journal of Natural Products. 67 (4): 675–677. doi:10.1021/np034066u. ISSN   0163-3864. PMID   15104502.
  12. 1 2 3 "New Active Ingredient and New Use Special Registration Reviews". Minnesota Department of Agriculture. Retrieved 2021-12-01.
  13. Hesselbach, Hannah; Scheiner, Ricarda (2018-03-21). "Effects of the novel pesticide flupyradifurone (Sivanto) on honeybee taste and cognition". Scientific Reports. 8 (1): 4954. Bibcode:2018NatSR...8.4954H. doi:10.1038/s41598-018-23200-0. ISSN   2045-2322. PMC   5862975 . PMID   29563522.