The nicotinic acetylcholine receptor (nAChR) is an ion-gated channel-type receptor mainly distributed in the ganglion and neuroskeletal muscle junctions. It is an important target for the development of neonicotinoid insecticides and analgesics.
The International Insecticide Resistance Action Committee (IRAC) classifies insecticides that act on nicotinic acetylcholine receptors in Group 4, which has 11 active ingredients and is divided into five subgroups. Seven neonicotinoid insecticides such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam are classified into Group4A; Group4B contains only nicotinic insecticide smoke. Alkali; Group4C, Group4D, Group4E all include only one active ingredient, which are sulfoximine insecticides flufenidamide, butenolide insecticide flupirfenone, mesoionic insecticide Trifluoropyrimidine. Among them, fluramide, flupirfenone and trifluoropyrimidine are new insecticides listed after 2011. This article outlines the mechanism, application, and development of these three insecticides that act on nicotinic acetylcholine receptors.
1 physical and chemical properties and toxicity
1.1 Physicochemical properties and toxicity of flunicarbamide
Sulfoxaflor is developed under the designation XDE208 and its chemical name is [methyl[1-(6-trifluoromethyl-3-pyridyl)ethyl]-λ6-sulfoxide alkenyl]cyanamide, CAS The accession number is 946578-00-3. Fluramide nitrile is a white solid with a melting point of 112.9 °C. Its solubility in water (20 ° C) was 0.568 g / L, the solubility in 1,2-dichloroethane was 39.6 g / L, and the solubility in methanol was 93.1 g / L.
The acute oral LD50 value of fluniconin nitrile in rats was 1,000 mg/kg, the acute percutaneous LD50 value was > 5,000 mg/kg, and the acute LD50 value for the mountain scorpion was 676 mg/kg; for rainbow trout (Oncorhynchus mykiss) The acute LC50 value (96h) was >101mg/L; the acute EC50 value (48h) for large sputum was >399mg/L.
Flunimidazole was highly toxic to bees. The acute exposure toxicity LD50 value (48h) was 0.379μg/bee, and the acute oral LD50 value (48h) was 0.146μg/bee. The acute oral and acute contact LD50 value (48h) of the preparation product 22% flonicamidonitrile SC to bees was 0.0601 μg/bee and 0.643 μg/bee, respectively. 22% flonicamidonitrile SC is highly toxic to bees and moderately risky to bees.
1.2 Fluoropyranone physicochemical properties and toxicity
Flupyradifurone developed under the code BYI02960, chemical name 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2-(5H)-one, The CAS registration number is 951659-40-8. Flupirfenone is a white to beige solid powder with a melting point of 69 °C. It has a solubility in water of 3.2 g/L and a solubility in methanol and ethyl acetate of >250 g/L (20 ° C).
Acute oral LD50 value of flupirfenolone in rats>300mg/kg, acute percutaneous LD50 value>2,000mg/kg, acute inhalation LC50 value>4.67mg/L, no irritation to rabbit skin and eyes, no cause Mutation and carcinogenesis. Flupirfenone is moderately toxic to birds, fish, and aquatic invertebrates.
The acute exposure LD50 value of flupirfenone to bees (48h) was >200μg/bee, which was low toxicity; the acute oral LD50 value was 1.2μg/bee. It is administered according to the recommended dosage of the label, which has no adverse effects on the foraging behavior of bees, the development of young bees and bee colonies, and can even be used in the flowering period of the crops.
1.3 Trifluorophenylpyrimidine physicochemical properties and toxicity
Triflumezopyrim was developed under the designation DPX-RAB55 and its chemical name is 3,4-dihydro-2,4-dioxo-1-(pyrimidin-5-ylmethyl)-3-(α,α , α-trifluorom-tolyl)-2H-pyrido[1,2-a]pyrimidin-1-indole-3- salt, CAS accession number 1263133-33-0, molecular formula C20H13F3N4O2, relative molecular mass 398.34 . Trifluoropyrimidine is a yellow crystal with a melting point of 188 to 198 °C. Its solubility in water is 0.284 g/L (20 ° C).
The acute oral LD50 value of trifluorophenylpyrimidine to P. sylvestris was 2,109 mg/kg, and the short-term feeding LD50 value was >935 mg/kg. The acute LC50 value (96h) for carp (Cyprinuscarpio) was >100 mg/kg. The EC50 value (48h) is >122mg/L.
Trifluoropyrimidine was highly toxic to bees. The acute contact LD50 value (48h) was 0.39μg/bee, and the acute oral LD50 value (48h) was 0.51μg/bee. It is low-toxic to the red cockroach, and the acute LC50 value (14d) is >1,000mg/kg.
2 applications
2.1 Application of flonicamidonitrile
Fluramide nitrile is a nicotinic acetylcholine receptor agonist. After binding to the receptor, it activates the intrinsic activity of the receptor, the receptor channel opens, and the Na+ outside the cell membrane flows into the cell, through the electrical signal transmission between the nerve cells. Control the function of the nervous system. It has a systemic activity of conduction, and after administration, it is transmitted from the bottom to the top through the xylem of the plant. Flufenidil nitrile has both stomach and contact toxicity, and has a wide spectrum of insecticides. It is effective against a variety of sucking mouthparts, such as the Hemiptera pest, the Homoptera pest, aphid, scale insect, planthopper, powder.è™±, for crops such as citrus, cotton, kale, flowers, vegetables and fruit trees. Flunimidazole is more active than other sucking mouthparts pest control agents such as neonicotinoid insecticides and has no cross-resistance with neonicotinoid insecticides including imidacloprid. It is highly efficient, fast and has a long-lasting effect. It can effectively control sucking mouthparts pests that are resistant to neonicotinoids, pyrethroids, organophosphorus and carbamate insecticides.
New insecticides pesticide assay field experiments conducted show: 7d, 50% fluorine sulfoxaflor water dispersible granules at 50 ~ 75g hm2 active ingredients / amounts, the control effect on cotton after drug mirid It is 85.37%～91.44%; under the dosage of 50～100g/hm2 active ingredient, the control effect against cotton whitefly is 80.37%～91.92%; under the dosage of 10～25g/hm2 active ingredient, the control effect on wheat aphid is 94.90% to 97.84%. The 22% flonicamidonitrile suspending agent has good control effect on apple jaundice, and has the characteristics of good quick-acting effect and long-lasting effect. Its recommended application mass fraction is 11-22 mg/kg.
From 2013 to 2016, the results of field efficacy trials conducted by Dow AgroSciences in China showed that 22% flonicamidil suspending agent was used in the amount of active ingredients of 36-45 g/hm2 for Chinese cabbage, potato aphid and cucumber. Melon and so on have good quick-acting and long-lasting effects. The 50% flonicamidonitrile water-dispersible granule has good quick-acting and long-lasting effect on watermelon melon under the dosage of 37.5～45g/hm2 active ingredient, and the control effect is 71.9%～99.7%.
When flunicarbamide is used to control cotton and cucumber whitefly, it should be applied in the beginning of the adult or the hatching period of the adult, and the control should be carried out twice on the 7th day after the first application. Uniform spray on the back; control of cotton blind mites, flunicarbamide should be applied 1 to 2 times in the young nymphs of blind mites, interval 7d, evenly sprayed against cotton stems and leaves; control of rice planthopper, flonicamid Nitrile should be applied once at the young nymphal stage of the planthopper, and evenly sprayed on the base of the stem and leaf of the rice plant; for the control of the scutellaria, the fluniguanamine should be applied once in the first generation of the nymphal nymph. The leaves are evenly sprayed.
The United States has strict regulations on the use of flunimycin: (1) it is allowed for crops that do not require bee pollination, such as barley, black wheat, wheat, lawn, etc.; (2) before harvesting of canola, bulbous plants, leafy vegetables, etc. Permitted to use; (3) crops attractive to bees, such as berry crops (grape, blueberry, cranberry), canola crops, vegetable crops (tomato, pepper, eggplant, okra), pear fruit crops , ornamental plants, etc., can be used after the flowering period.
2.2 Application of flurbifuranone
Flupirfenone is also a nicotinic acetylcholine receptor agonist. After binding to a receptor protein, it activates a receptor to produce a biological reaction, induces a depolarized ion current, and causes the nerve cell to be in an excited state. After poisoning, insects usually show signs of nervous excitement, body tremors, and uncoordinated movements. Flupirfenone has systemic conduction activity, and the active ingredient can be transmitted to the top through the xylem, or in the direction of the transpiration stream, and can also be distributed to adjacent plant cells by vertical permeation. Therefore, it can effectively control pests in shelter. Flupirfenolone is flexible in application, foliar spray, soil watering or drip irrigation, and can also be used for seed treatment. When used for foliar spray, it is absorbed through the leaves and stems; when applied, it is absorbed through the roots. Flubepirone has a wide pot life and can even be applied at the flowering stage, making it safe for crops at all stages of growth.
Flupirfenone can be used in vegetables, fruit trees, coffee, cocoa, cotton, soybeans (seed treatment) and other field crops to control the main sucking mouthworms such as aphids, whiteflies, hibiscus and leaves. Earthworms, scale insects, beetles, leaf miners, whiteflies, soft mites, citrus psyllids, weevils and thrips are effective against all growing pests, including larvae and adults. The amount is determined according to the type of crop and the canopy of the fruit tree, and the effective ingredient is usually 50-200 g/hm2.
The field test results of new insecticides from 2013 to 2014 showed that 200g/L flupirfenone solution has good control effect on B. tabaci on protected tomato, and it has good quick-acting effect and long-lasting effect. The control effect in the last 3 days was 92.87% to 95.87%. The 200 g/L flupirfenone solution is recommended for spray application in the early stage of B. tabaci.
Hu Yuqing et al. evaluated the control effect of flupirfenone on citrus hibiscus. The 17% flupirfenone solution showed good quick-acting and long-lasting effect on citrus hibiscus. When the active ingredient mass fraction was 50-100mg/kg, the control effect was higher after 3, 7 and 14d. 88.5%, the control effect of 21d after the drug remained at 98.4% ~ 100%. The 17% flupirfenone solution is suitable for spraying at a dose of 50-100 mg/kg when the citrus shoots are taken out and the citrus psyllids are first.
Although flupirfenone also acts on the nicotinic acetylcholine receptor of insects, it has novel pharmacophores, such as brand new crotonic lactone groups, unique difluoro side chain groups, and therefore Neonicotinoid insecticides have little or no cross-resistance and are suitable for pest resistance management (IRM) and integrated pest management (IPM).
Flupirfenone is highly selective for most beneficial organisms in fruit trees and vegetables, has no adverse effects on non-target arthropods, and has high safety.
2.3 application of trifluoropyrimidine
Trifluoropyrimidine is the only inhibitory compound in the insecticide that acts on the nicotinic acetylcholine receptor, the nicotinic acetylcholine receptor inhibitor. After insect poisoning, it is stagnant, without excitement or paralysis, followed by paralysis and paralysis until death. It has good systemic conductivity, permeability and resistance to rain erosion. Trifluoropyrimidine is highly efficient and broad-spectrum, and has good control effect against lepidopteran and homopteran pests. It can be used in crops such as cotton, rice, corn and soybean. At present, Dow DuPont develops it for rice, and controls rice planthoppers, spider mites, etc., especially for the control of brown planthopper (Nilaparvatalugens). Trifluoropyrimidine can be used for both foliar spray and soil treatment.
According to the field test results of new pesticides in 2013-2014, 10% trifluoropyrimidine suspension (trade name) has good control effect on rice planthopper and is safe for rice. When the active ingredient dosage is 20-25 g/hm2, the control effect is 94.55%-99.80%; after 21 days, the control effect remains above 90.98%.
The agricultural machinery extension station in Miluo City, Hunan Province is based on the high resistance of imidacloprid and pymetrozine to the drug, and the field efficacy test was carried out with a new 10% trifluoropyrimidine suspension. When the active ingredient dosage was 25g/hm2, the corrected control effect of 10% trifluoropyrimidine suspension on 3~25d after brown planthopper was 92.94%-99.55%; the agent was safe for rice growth and had no inhibitory effect on spider population. The 10% trifluoropyrimidine suspension can not only effectively control brown planthopper, gray planthopper and white backed planthopper, but also has a long-lasting effect, fast action, safety to natural enemies, and can significantly improve rice yield and quality.
10% trifluoropyrimidine suspension is suitable for uniform spraying of crop stems and leaves in rice vegetative growth period (before tillering to early panicle differentiation) and rice nymphs at the beginning of nymph; other effects are selected after 21~25d The mechanism of the product is controlled to remove residual locusts.
Due to long-term, large-scale drug use, rice planthopper produces different degrees of resistance to common agents such as imidacloprid, pymetrozine, and thiamethoxam. Some of the agents have a level of resistance above moderate, and trifluoropyrimidines and groups (including new Nicotinic insecticides and other insecticides outside the group have no cross-resistance. Therefore, it is suitable for use in resistance management.
3 development situation
3.1 Development of flonicamidonitrile
In November 2011, fluramide was first registered in South Korea and was launched in South Korea in the first half of 2012 for some fruits and vegetables under the trade name Isoclast.
In 2013, flonicamid was registered in the United States and Canada under the trade names Closer and Transform. In the same year, it was also registered in Panama, Guatemala, Indonesia and Vietnam.
Although fluramide has been registered in the United States for barley, vegetables, citrus, cotton, canola, soybeans, wheat, etc., in view of its potential risk to bees, the US Environmental Protection Agency cancelled fluramide in 2015. Nitrile registration in the United States. In 2017, Isoclast received emergency exemption rights in nine states, including Arkansas, Florida, and Louisiana, for the control of Melanaphissacchari on sorghum.
In 2015, fluramide was officially registered in the European Union and is valid until August 18, 2025. As of June 2018, fluramide has been registered in countries such as Ireland, the Czech Republic, France, and Slovakia. The registered EU member states include Austria, Bulgaria, Spain, Hungary, Italy, the Netherlands, and the United Kingdom. The drafting country is also the first EU member state to approve the registration of flonicamid.
In 2013, the fluramide and the two single-dose products were temporarily registered in China and officially registered in 2016. Formulation product 22% flonicamidil suspension (trade name Teflon) is registered for rice, cucumber, cabbage, citrus, apple, grape, peach and so on. 50% flonicamidonitrile water-dispersible granules (trade name can be applied) for the control of cotton blind mites, whitefly, aphids and peach trees, watermelons, wheat aphids and so on.
In 2017, flonicamid is also registered in countries such as Australia for nuts and avocados.
Flumazenil nitrile 2013 global sales of $ 55 million, global sales in 2014 reached $ 90 million, global sales in 2015 fell to $ 80 million, global sales in 2016 increased to $ 105 million, an increase of 31.3 %.
In 2016, the North American Free Trade Zone was the largest regional market for flonicamid, with sales in the region of $16 million, accounting for 15.3% of the global market; Asia ranked second with sales of $13 million. It accounts for 12.0% of the total market. The United States is the largest drug-using country for fluramide, with US sales of US$16 million in 2016, accounting for 15.3% of total sales. The grain is the first large-scale crop of fluramide, and the sales of fluramide in 2016 were US$ 9.43 million, accounting for 9.0% of total sales; cotton and soybeans ranked 2nd and 3rd. Sales were $8.98 million and $7.95 million, respectively, accounting for 8.6% and 7.6% of total sales.
3.2 Development of flurbifuranone
In 2014, Bayer first launched the flupirfenone-based SivantoPrime in Honduras and Guatemala for the control of sucking mouthparts on crops such as tomatoes, peppers, potatoes, cucumbers, watermelons and citrus. In the same year, flupirfenone was also marketed in Dominica and Costa Rica.
In 2015, flupirfenone was marketed in the United States, Mexico and Nicaragua. Its preparation product, Sivanto200SL, is registered in the United States for use in fruit trees, vegetables and most field crops to control sucking mouthparts pests.
In November 2015, Bayer's two flupirfenone products, SivantoPrime and BYI02960480FS, were officially registered in Canada. The former is foliar spray or soil treatment for crops such as fruit trees and vegetables; the latter is used as a seed treatment agent for soybeans.
In 2015, flupifuranone was included in the list of registered active ingredients in the EU Pesticide Registration Regulations (1107/2009), valid until December 9, 2025. The Netherlands is a drafting country for documents. At present, the product has not been registered in EU member states. The countries that are registered are Austria, Bulgaria, Czech Republic, Estonia, Spain, Finland, Hungary, Ireland, Italy, Latvia, Netherlands, Sweden, Slovenia and Slovakia.
On November 14, 2016, Bayer AG's 96% flupirfenone and 17% flupirfenone solution were temporarily registered in China, but the current period of validity has expired.
In addition, Bayer is applying for registration of flupirfenone in Australia for vegetables, fruit trees, coffee, cocoa, cotton, soybeans and other field crops.
Currently, flupirfenone is still in the early stages of commercial development, with 2016 global sales of $5 million.
Development of 3.3 trifluorophenylpyrimidine
On January 7, 2017, DuPont's 96% trifluoropyrimidine and 10% trifluoropyrimidine suspension (trade name) were approved for temporary registration in China; on August 31, 2017, the two products were China is approved for official registration. The preparation product is registered for the control of rice planthopper, and the active ingredient is used in the amount of 16-25 g/hm2, which is used for foliar spray.
Dow DuPont has submitted registration data for trifluoropyrimidine to major rice growers around the world.
To date, trifluoropyrimidine has not been registered in the United States and the European Union.
Trifluorophenylpyrimidine is still in the early stages of commercial development, with 2016 global sales of $1 million.
4 summary
In 2016, the global market share of pesticides was US$16.459 billion, accounting for 29.2% of the global pesticide market. Despite the influence of bee venom, EU countries have restricted the use of some neonicotinoid insecticides, but seven neonicotinoid insecticides such as thiamethoxam and imidacloprid still achieved global sales of US$3 billion in 2016. 18.2% of the global pesticide market. Among the top 15 pesticide species in the world in 2016, neonicotinoid insecticides acting on nicotinic acetylcholine receptors accounted for 4 seats. Neonicotinoid insecticides are all varieties that have been marketed since the 1990s and can achieve such market performance, which is related to their good selectivity, novel mechanism of action, excellent control effect, and extensive insecticidal spectrum. .
Flufenidamide, flupirfenone, and trifluorophenylpyrimidine are all new insecticides that act on nicotinic acetylcholine receptors after 2011. Similar to other traditional neonicotinoid insecticides that act on nicotinic acetylcholine receptors, all of which have good systemic activity and are highly effective against a variety of sucking mouthparts, for mammals, fish, birds, etc. Low toxicity; due to its special mechanism of action, the three can be used to control pests that are resistant to organophosphorus, carbamate, pyrethroid insecticides; in addition, to nicotinic acetylcholine receptors In addition to crops, pesticides can also be used in non-agricultural fields, and the market is vast; their use in developing countries may increase. In view of the above points, the market for three new insecticides that act on nicotinic acetylcholine receptors is expected.
Flunimidazole and trifluoropyrimidine are highly toxic to bees. Therefore, when applied in the field, measures should be taken to reduce the risk of toxicity to bees. In the future, fluramide and trifluoropyrimidine will still be affected by bee venom. In some developed countries, some crops or seed treatment will be restricted, and the market will be restrained.
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(Source: Pesticide Newsletter)
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