Diafenthiuron

Last updated
Diafenthiuron
Diafenthiuron.svg
Names
IUPAC name
1-tert-Butyl-3-[4-phenoxy-2,6-di(propan-2-yl)phenyl]thiourea
Other names
1-tert-Butyl-3-(2,6-diisopropyl-4-phenoxyphenyl)thiourea
Identifiers
3D model (JSmol)
8343025
ChEBI
ChemSpider
ECHA InfoCard 100.113.249 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 616-885-7
KEGG
PubChem CID
RTECS number
  • XN9100000
UNII
  • InChI=1S/C23H32N2OS/c1-15(2)19-13-18(26-17-11-9-8-10-12-17)14-20(16(3)4)21(19)24-22(27)25-23(5,6)7/h8-16H,1-7H3,(H2,24,25,27)
    Key: WOWBFOBYOAGEEA-UHFFFAOYSA-N
  • CC(C)C1=CC(=CC(=C1NC(=S)NC(C)(C)C)C(C)C)OC2=CC=CC=C2
Properties
C23H32N2OS
Molar mass 384.58 g·mol−1
Hazards
GHS labelling: [1]
GHS-pictogram-skull.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H331, H332, H373, H410
P260, P261, P271, P273, P304+P340, P316, P317, P319, P321, P391, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Diafenthioron is a pesticide, specifically an insecticide. Diafenthiuron is sold under the brand names Derby, Diron, Pegasus, Polar and Polo.

Contents

History

Diafenthiuron was introduced to the market in 1990 by a pharmaceutical company called Ciba-Geigy in Switzerland and due to rising environmental concerns it is no longer approved in Switzerland and other countries of the European Union. [2] However, until 2001, Switzerland still produced and exported the compound to other countries where its use as an agricultural pesticide was still legal. [3] [4]

Structure and reactivity

Diafenthiuron is an phenol ether of molecular weight 384.6 g/mole and containing two 6-carbon rings attached to an oxygen and nitrilo (tert-butylcarbamate) group substituting for a hydrogen atom at position 2. It is highly soluble in multiple organic solvents however dissolves poorly in aqueous solutions due to the hydrocarbon rich regions and oxygen atom which do not form H bonds with water molecules. [5] Therefore diafenthiuron contamination of underground water storages by leaching is unlikely. Its lack of water solubility (partition coefficient logPow = 5.76) and strong sorption capacity, means it has the ability to accumulate persistently in aquatic and soil systems. [2]

It is a broad spectrum, both systemic and contact as well as stomach activity synthetic pesticide impairing mitochondrial function in target pests (phytophagous mites). [6] [7] Due to progressive break-down of diafenthiuron to non-toxic metabolites, it poses no significant reactivity threat in the field of ecotoxicology (Hazard class III = slightly hazardous). However, its highly reactive metabolite carbodiimide (a result of S-oxidation → either non-enzymatic (light-catalyzed), P450 monooxygenases, or by FAD monooxygenases) binds to the mitochondrial ATPase and porin, inhibiting ATP production. [8]

Synthesis

The synthesis of diafenthiuron starts with phenol reacting with 2,6-diisopropyl-4-chloroaniline, creating the intermediate product 2,6-diisopropyl-4-phenoxyaniline. 2,6-diisopropyl-4-phenoxyaniline will then undergo a reaction with thiophosgene and form N-(2,6-diisopropyl-4-phenoxyphenyl)isothiocyanate. This in turn will react with tert-butylamine and form diafenthurion. [9]

Synthesis of Diafenthiuron Diafenthiuron synthesis.svg
Synthesis of Diafenthiuron

Mechanism of action

Diafenthiuron is photochemically or metabolically transformed into a highly reactive metabolite, Diafenthiuron carbodiimide, which covalently and irreversibly binds to microsomal glucose-6-phosphate translocase, a part of the adenosine triphosphatase (ATPase) complex. It is the only insecticide in IRAC group 12A. The binding inhibits the function of the ATPase complex due to the modification of a single sulfhydryl/amino phosphate group of the glucose-6-phosphate translocase. Therefore, substrates such as inorganic phosphate, carbamoyl phosphate and pyrophosphate cross the microsomal membrane freely without the catalytic function of the translocase; ATP production is inhibited. [6] Diafenthiuron carbodiimide also affects mitochondrial porins, but due to the fact that the function of these mitochondrial porins is not fully known yet, the effects of the carbodiimide on these porins is also not understood. In summary, diafenthiuron inhibits the process of mitochondrial respiration by binding to various mitochondrial components.

Efficacy and side effects

Efficacy

Diafenthiuron has shown high efficacy against many important agricultural pests, including mites, aphids, thrips, and whiteflies. Several studies have demonstrated the efficacy of diafenthiuron in controlling various pests affecting a variety of crops. For example, diafenthiuron has shown to be effective against cotton bollworm, cotton jassid, and spider mites. [10] With citrus fruits, it has been shown to control citrus rust mites and aphids. [11] [12] With grapes, diafenthiuron has shown to be effective against grape leafhoppers and mites. [13] The efficacy of diafenthiuron is dependent on several factors; the target pest species, the stage of the pest's life cycle, and environmental conditions such as temperature and humidity. Next to that, the repeated use of diafenthiuron can lead to the development of resistance in target pests, reducing the efficacy of the insecticide over time.

Side effects

Apart from enzymatic conversion, diafenthiuron readily dissolves in organic solvents or is broken down by sunlight into two major by-products; diafenthiuron carbodiimide and diafenthiuron urea. In aqueous systems, the carbodiimide was further observed to be photo-transformed into diafenthiuron urea in the presence of sunlight; a key photolysis pathway in diafenthiuron breakdown in the environment. [14]

Due to aerial application of the pesticide, its entering into fresh water bodies has observable effects on non-target organisms. Sub lethal doses (0.0075 mg/L) in both short and long term application had significant adverse effects on serum, hematological and elemental concentrations of fish which suggests that the use of diafenthiuron as a pesticide threatens the stability of aquatic food webs. [15] The second metabolite, urea, puts an additional strain on aquatic systems.

Rapid photodegradation of diafenthiuron and its metabolites in water and soil suggests limited accumulation capacity, despite the bioaccumulation potential of ~800. However, a pond mesocosm study did not exhibit such effects in vivo, possibly due to the rapid time period needed for degradation of 50% of the product (DT50) being <22 hours. [16] This considerably decreases the time frame of possible exposure and therefore reduces inducible toxicity by diafenthiuron metabolism.

Toxicology assessments and evaluations of dietary intake residues suggest that there are no adverse effects on human health due to exposure to agricultural residues of diafenthiuron application. [16]

Toxicity data

Toxicity data [2]
MeasurementMethod of administrationLD50
1 Acute toxicity datainhalation (rat)558 mg/m3
2 Acute toxicity dataoral (duck)>1500 mg/kg
3 Acute toxicity dataoral (quail)>1500 mg/kg
4 Acute toxicity dataoral (rat)2068 mg/kg
5 Acute toxicity dataskin (rat)>2 gm/kg
6 Other multiple dose dataoral (dog)lowest published dose: 360 mg/kg/90D continuous

Effects on animals

When animals are exposed to diafenthiuron, both acute and chronic effects can occur. Different animal species can have different sensitivity to diafenthiuron depending on factors like size, metabolism, and exposure pathway. However, in general, aquatic organisms and bees suffer most from diafenthiuron exposure.

Aquatic life

Diafenthiuron can have adverse effects on aquatic life when it enters water bodies through runoff or spray drift. The effects depend on the concentration and duration of exposure, as well as the sensitivity of the aquatic species. Some potential effects of diafenthiuron include:

  1. Acute toxicity: diafenthiuron can be highly toxic, especially to invertebrates such as crustaceans and insects. Exposure to high concentrations of diafenthiuron can cause rapid death in these organisms. [17]
  2. Chronic toxicity: prolonged exposure to lower concentrations of diafenthiuron can lead to chronic effects. These effects can include reduced growth and reproduction, as well as changes in behavior and physiology. [18]

Bees

Bees can be exposed to diafenthiuron through the consumption of contaminated nectar and pollen. This can have adverse effects on health and survival. The effects of diafenthiuron on bees can include:

  1. Reduced foraging activity: exposure to diafenthiuron can cause behavioural changes in bees, reducing their foraging activity and impairing their ability to locate and collect food. [19]
  2. Reduced reproduction: exposure to diafenthiuron can reduce reproductive success, including the production of eggs and the survival chances of larvae. [20]
  3. Mortality: high levels of exposure to diafenthiuron can cause rapid mortality, especially in young or weak individuals. [19]

Related Research Articles

<span class="mw-page-title-main">Pesticide</span> Substance used to destroy pests

Pesticides are substances that are used to control pests. They include herbicides, insecticides, nematicides, fungicides, and many others. The most common of these are herbicides, which account for approximately 50% of all pesticide use globally. Most pesticides are used as plant protection products, which in general protect plants from weeds, fungi, or insects. In general, a pesticide is a chemical or biological agent that deters, incapacitates, kills, or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, or spread disease, or are disease vectors. Along with these benefits, pesticides also have drawbacks, such as potential toxicity to humans and other species.

<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. The major use of insecticides is in agriculture, but they are also used in home and garden settings, industrial buildings, for vector control, and control of insect parasites of animals and humans.

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

Cypermethrin (CP) is a synthetic pyrethroid used as an insecticide in large-scale commercial agricultural applications as well as in consumer products for domestic purposes. It behaves as a fast-acting neurotoxin in insects. It is easily degraded on soil and plants but can be effective for weeks when applied to indoor inert surfaces. It is a non-systemic and non-volatile insecticide that acts by contact and ingestion, used in agriculture and in pest control products. Exposure to sunlight, water and oxygen will accelerate its decomposition. Cypermethrin is highly toxic to fish, bees and aquatic insects, according to the National Pesticide Information Center (NPIC) in the USA. It is found in many household ant and cockroach killers, including Raid, Ortho, Combat, ant chalk, and some products of Baygon in Southeast Asia.

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

Bifenthrin is a pyrethroid insecticide. It is widely used against ant infestations.

<span class="mw-page-title-main">Permethrin</span> Medication and insecticide

Permethrin is a medication and an insecticide. As a medication, it is used to treat scabies and lice. It is applied to the skin as a cream or lotion. As an insecticide, it can be sprayed onto outer clothing or mosquito nets to kill the insects that touch them.

<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 discontinued in 1991.

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

Fipronil is a broad-spectrum insecticide that belongs to the phenylpyrazole insecticide class. Fipronil disrupts the insect central nervous system by blocking the ligand-gated ion channel of the GABAA receptor and glutamate-gated chloride (GluCl) channels. This causes hyperexcitation of contaminated insects' nerves and muscles. Fipronil's specificity towards insects is believed to be due to its greater binding affinity for the GABAA receptors of insects than to those of mammals, and for its action on GluCl channels, which do not exist in mammals. As of 2017, there does not appear to be significant resistance among fleas to fipronil.

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

Fenthion is an organothiophosphate insecticide, avicide, and acaricide. Like most other organophosphates, its mode of action is via cholinesterase inhibition. Due to its relatively low toxicity towards humans and mammals, fenthion is listed as moderately toxic compound in U.S. Environmental Protection Agency and World Health Organization toxicity class.

<span class="mw-page-title-main">Dichlorvos</span> Insect killing chemical, organophosphate

Dichlorvos is an organophosphate widely used as an insecticide to control household pests, in public health, and protecting stored products from insects. The compound has been commercially available since 1961. It has become controversial because of its prevalence in urban waterways and the fact that its toxicity extends well beyond insects. Since 1988, dichlorvos cannot be used as a plant protection product in the EU.

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">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">Environmental impact of pesticides</span> Environmental effect

The environmental effects of pesticides describe the broad series of consequences of using pesticides. The unintended consequences of pesticides is one of the main drivers of the negative impact of modern industrial agriculture on the environment. Pesticides, because they are toxic chemicals meant to kill pest species, can affect non-target species, such as plants, animals and humans. Over 98% of sprayed insecticides and 95% of herbicides reach a destination other than their target species, because they are sprayed or spread across entire agricultural fields. Other agrochemicals, such as fertilizers, can also have negative effects on the environment.

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

Etofenprox is a pyrethroid derivative which is used as an insecticide. Mitsui Chemicals Agro Inc. is the main manufacturer of the chemical. It is also used as an ingredient in flea medication for cats and dogs.

<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">Propargite</span> Chemical compound

Propargite is a pesticide used to kill mites. It acts through inhibition of mitochondrial ATP synthase, and is in IRAC group 12C. Symptoms of excessive exposure are eye and skin irritation, and possibly sensitization. It is highly toxic to amphibians, fish, and zooplankton, as well as having potential carcinogenity.

<span class="mw-page-title-main">Naled</span> Organophosphate insecticide

Naled (Dibrom) is an organophosphate insecticide. Its chemical name is dimethyl 1,2-dibromo-2,2-dichloroethylphosphate.

<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">Novaluron</span> Chemical compound

Novaluron, or (±)-1-[3-chloro-4-(1,1,2-trifluoro-2-trifluoro- methoxyethoxy)phenyl]-3-(2,6-difluorobenzoyl)urea, is a chemical with pesticide properties, belonging to the class of insecticides called insect growth regulators. It is a benzoylphenyl urea developed by Makhteshim-Agan Industries Ltd.. In the United States, the compound has been used on food crops, including apples, potatoes, brassicas, ornamentals, and cotton. Patents and registrations have been approved or are ongoing in several other countries throughout Europe, Asia, Africa, South America, and Australia. The US Environmental Protection Agency and the Canadian Pest Management Regulatory Agency consider novaluron to pose low risk to the environment and non-target organisms and value it as an important option for integrated pest management that should decrease reliance on organophosphorus, carbamate and pyrethroid insecticides.

References

  1. ↑ "Diafenthiuron". pubchem.ncbi.nlm.nih.gov.
  2. 1 2 3 PubChem. "Diafenthiuron". pubchem.ncbi.nlm.nih.gov. Retrieved 2023-03-19.
  3. ↑ "Public Eye et al. vs. Syngenta". OECD Watch. Retrieved 2023-03-19.
  4. ↑ "Strengere Bestimmungen für die Ausfuhr von Pflanzenschutzmitteln". www.admin.ch. Retrieved 2023-03-19.
  5. ↑ "Physical Properties of Ether". Chemistry LibreTexts. 2015-08-07. Retrieved 2023-03-19.
  6. 1 2 Ruder, F. J.; Kayser, H. (1993-06-01). "The Carbodiimide Product of Diafenthiuron Inhibits Mitochondria in Vivo". Pesticide Biochemistry and Physiology. 46 (2): 96–106. doi:10.1006/pest.1993.1041. ISSN   0048-3575.
  7. ↑ "HPM Chemicals & Fertilizers Ltd". hpmindia.com. Retrieved 2023-03-19.
  8. ↑ "Diafenthiuron". Grainews. Retrieved 2023-03-19.
  9. ↑ Unger, Thomas A. (1996-12-31). Pesticide Synthesis Handbook. William Andrew. ISBN   978-0-8155-1853-2.
  10. ↑ Bajya, D. R.; Ranjith, M.; Lakharan, M. C.; Raza, S. (2016). "Efficacy of Diafenthiuron 47.8 SC Against Sucking Pests of Cotton and ITS Safety to Natural Enemies". Indian Journal of Entomology. 78: 15. doi:10.5958/0974-8172.2016.00003.1. S2CID   74829355.
  11. ↑ Bagwani, Krishi (2015). "Journal of Eco-friendly Agriculture" (PDF). Journal of Eco-friendly Agriculture. 10 (2): 172–174.
  12. ↑ Dalvaniya, D.; Patel, P.; Pareek, A.; Panickar, B. (2015). "Efficacy of some insecticides against citrus psylla, Diaphorina citri Kuwayama on kagzi lime". Journal of Entomological Research. 39 (2): 141. doi:10.5958/0974-4576.2015.00009.2. S2CID   88094758.
  13. ↑ Assessment, US EPA National Center for Environmental (2009-03-15). "Bioefficacy of diafenthiuron 50 SC (Polo 50 SC) against grapevine pests and its effect on natural enemies and plants". hero.epa.gov. Retrieved 2023-03-19.
  14. ↑ Keum, Young-Soo; Kim, Jeong-Han; Kim, Yong-Whan; Kim, Kyun; Li, Qing X. (May 2002). "Photodegradation of diafenthiuron in water". Pest Management Science. 58 (5): 496–502. doi:10.1002/ps.483. ISSN   1526-498X. PMID   11997978.
  15. ↑ Riaz-Ul-Haq, Muhammad; Javeed, Rabia; Iram, Saman; Rasheed, Muhammad Arslan; Amjad, Muhammad; Iqbal, Furhan (September 2018). "Effect of Diafenthiuron exposure under short and long term experimental conditions on hematology, serum biochemical profile and elemental composition of a non-target organism, Labeo rohita". Environmental Toxicology and Pharmacology. 62: 40–45. doi:10.1016/j.etap.2018.06.006. ISSN   1872-7077. PMID   29957367. S2CID   49601487.
  16. 1 2 Arney, Malcolm (1996). Diafenthiuron. National registration authority.
  17. ↑ Gao, Y.-N (September 2010). "Risk assessment of diafenthiuron to three species of aquatic organisms". Journal of Ecology and Rural Environment. 26 (5): 487–491 – via ResearchGate.
  18. ↑ Su, Menglan; Bao, Rongkai; Wu, Yaqing; Gao, Bo; Xiao, Peng; Li, Wenhua (May 2023). "Diafenthiuron causes developmental toxicity in zebrafish (Danio rerio)". Chemosphere. 323: 138253. Bibcode:2023Chmsp.323m8253S. doi:10.1016/j.chemosphere.2023.138253. ISSN   1879-1298. PMID   36849025. S2CID   257209777.
  19. 1 2 Stanley, Johnson; Chandrasekaran, Subramanian; Preetha, Gnanadhas; Kuttalam, Sasthakutty (May 2010). "Toxicity of diafenthiuron to honey bees in laboratory, semi-field and field conditions". Pest Management Science. 66 (5): 505–510. doi:10.1002/ps.1900. ISSN   1526-4998. PMID   20069631.
  20. ↑ Stuligross, Clara; Williams, Neal M. (2021-11-30). "Past insecticide exposure reduces bee reproduction and population growth rate". Proceedings of the National Academy of Sciences of the United States of America. 118 (48): e2109909118. Bibcode:2021PNAS..11809909S. doi: 10.1073/pnas.2109909118 . ISSN   1091-6490. PMC   8640752 . PMID   34810261.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.