DESC:FIELD OF THE INVENTION:
The present invention relates to a synergistic insecticidal composition comprising A) Afidopyropen B) at least one insecticide selected from diafenthiuron, pyriproxyfen and spiromesifen C) at least one more insecticide selected from 5 acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite, cartap hydrochloride, 10 thiocyclam hydrogen oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin with one or more inactive excipients. The present 15 invention also relates to process for preparing the said composition and its use in crops. BACKGROUND OF THE INVENTION 20 Afidopyropen was first disclosed in EP1889540B1. Afidopyropen, chemically known as [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-(cyclopropylcarbonyloxy)- 1,2,3,4,4a,5,6,6a,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3- pyridyl)-11H,12H-benzo [f] pyrano[4,3-b]chromen-4-yl]methyl cyclopropanecarboxylate and having chemical structure as below; 25
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Afidopyropen, modulates chordotonal organs of American grasshoppers (Schistocerca americana) in the same fashion. Afidopyropen stimulated heterologously expressed TRPV channels from two different insect species - fruit fly (Drosophila melanogaster) and pea aphid (Acyrthosiphon pisum) - but did not affect function of the mammalian TRPV channel TRPV4. 5
Diafenthiuron was first disclosed in GB2060626. Diafenthiuron, chemically known as 1-tert-butyl-3-(2,6-di-isopropyl-4-phenoxyphenyl)thiourea or N-[2,6-bis(1-methylethyl)-4-phenoxyphenyl]-N'-(1,1-dimethylethyl)thiourea and having chemical structure as below; 10
Diafenthiuron acts after conversion by either light, or in vivo, to the corresponding carbodiimide, which is an inhibitor of mitochondrial respiration. Mode of action as insecticide and acaricide which kills larvae, nymphs and adults is by contact and/or stomach action; also shows some ovicidal action. It is commonly used as insecticide 15 and acaricide effective against phytophagous mites (tetranychidae, tarsonemidae), aleyrodidae, aphididae and jassidae on cotton, various field and fruit crops, ornamentals and vegetables. Also controls some leaf-feeding pests in cole crops (Plutella xylostella), soya beans (Anticarsia gemmatalis) and cotton (Alabama argillacea). 20
Pyriproxyfen was first disclosed in US 4,751,225. Chemically known as 4-Phenoxyphenyl 2-(2-pyridyloxy)propyl ether and chemical structure is as below;
Pyriproxyfen is a pyridine-based pesticide which is found to be effective against a 25 variety of arthropoda. It was introduced to the US in 1996, to protect cotton crops
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against whitefly. It has also been found useful for protecting other crops. It is also used for prevention of fleas on household pets. Pyriproxyfen is a juvenile hormone analog and a relatively stable aromatic compound. It functions as an insecticide by overloading the hormonal system of the target insect, ultimately affecting egg production, brood care and other social interactions, and inhibiting growth. 5
Spiromesifen was first disclosed in US6436988. Spiromesifen is chemically known as 3,3-Dimethyl butanoic acid 2-oxo-3-(2,4,6-trimethylphenyl)-1-oxaspiro[4.4]non-3-en-4-yl ester and chemical structure is as below;
10
Spiromesifen is a novel insecticidal/acaricidal compound derived from spirocyclic tetronic acids that acts effectively against whiteflies and mites via inhibition of acetyl-CoA-carboxylase, a lipid metabolism enzyme. Spiromesifen is an insecticide from the new class of spirocyclic tetronic acids that acts effectively against whiteflies and mites. It acts as an inhibitor of acetyl-CoA-carboxylase, a lipid 15 metabolism enzyme, and causes a significant decrease in total lipids. This compound has been introduced in several countries over the last few years and is becoming an important compound for controlling whiteflies and mites in resistance management programmes, along with other effective insecticides such as neonicotinoids and diafenthiuron. Several recent studies have shown the 20 effectiveness of spiromesifen against whiteflies and mites.
WO2015120684A1 describes synergistic pesticidal composition has active components afidopyropen and pymetrozine, and the mass ratio of the afidopyropen to the pymetrozine is 1:80 to 80:1. The composition has a significant synergistic 25 effect, has significantly-enhanced pesticidal activity compared with a single agent, and has a very good preventing effect on multiple kinds of pests such as planthoppers, leafhoppers, whiteflies, and thrips.
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WO2016038067A1 discloses agricultural methods for controlling pests and/or increasing the plant health of cultivated plants having at least one modification, by treating such cultivated plants, parts of such plants, plant propagation materials or their locus of growth with afidopyropen or compositions comprising afidopyropen 5 or mixtures of afidopyropen with another pesticidal active ingredient.
WO 2010/020477 describes insecticidal compositions comprising Diafenthiuron and a crop safener, and to the use of such compositions in controlling insects in crops of useful plants. The invention further extends to combination packages of 10 Diafenthiuron and crop safener.
CN106538587A discloses a pesticide combination containing afidopyropen and pyriproxyfen. In the combination, the weight ratio of the afidopyropen to the pyriproxyfen ranges from (1 to 40) to (40 to 1); the pesticide combination disclosed 15 by the invention is particularly used for preventing and treating injurious insects including aleyrodid, thrip, aphids, plant hoppers and the like. The pesticide combination disclosed by the invention can be processed into any one dosage form with the help of a conventional auxiliary agent used in a pesticide preparation processing process and the dosage form is selected from any one of missible oil, 20 wettable powder, water dispersible granules, a suspending agent, emulsion in water, micro-emulsion, a dispersible oil suspending agent, a micro-capsule suspending agent and water soluble powder.
CN105941437A discloses a compound insecticide containing afidopyropen and 25 fipronil. Living and physiological habits of bemisia tabaci and different insecticidal mechanisms of various insecticides are perfectly combined together, an appropriate auxiliary and an appropriate carrier are supplemented, and an appropriate ratio is sought for preventing and controlling the bemisia tabaci. Compared with the traditional water prevention and control method, the compound insecticide has the 30 following advantages: a) the compound insecticide has obvious synergistic effect on the bemisia tabaci compared with a single dosage, and control efficacy can be
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obviously improved; b) part of middle-high-toxicity insecticides can be replaced, dosage is reduced, and environmental pollution and agricultural product residue are reduced; c) insecticide resistance of the bemisia tabaci to a single insecticide can be delayed; and d) lasting period is long, and cost can be reduced compared with a single insecticide 5
CN106305762A discloses a synergistic insecticidal composite containing afidopyropen, containing the effective components of afidopyropen(A) and nereistoxin insecticide(B), wherein B is chosen from monosultap, bisultaaqueous or cartap; the mass ratio of A and B is 40:1-1:80, and the total mass percent of 10 effective components in composite is 15%-85%. The composite can be formulated into agriculture-allowed suspension concentrate, suspoemulsion, microemulsion, water power, wettable powder, soluble power, aqueous capsule suspension or dispersible oil suspension concentrate. This invention combinaiton is reasonable. It has control effects on such piercing and sucking insects and those with rasping 15 sucking mouthparts as plant hoppers and thrips which feed on paddies and vegetables. Compared to the current agent with single component, it has significant effects. It reduces the use dosage with features of efficient cost and environmental protection.
20 However still there is a need for an insecticidal composition which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.
Inventors of the present invention have surprisingly found that the a synergistic 25 insecticidal composition comprising A) Afidopyropen B) at least one insecticide selected from diafenthiuron, pyriproxyfen and spiromesifen C) at least one more insecticide selected from acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradifurone, 30 triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite,
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cartap hydrochloride, thiocyclam hydrogen oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin with one or more inactive excipients described herein in 5 can provide solution to the above mentioned problems. SUMMARY OF THE INVENTION It is an aspect of the present invention is to provide, with a view to effective 10 resistance management and effective control of phytopathogenic harmful insects, at application rates which are as low as possible, compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful pests and a broadened activity spectrum, in particular for certain indications. 15
We have accordingly found that this object is achieved by the present a synergistic insecticidal composition comprising A) Afidopyropen B) at least one insecticide selected from diafenthiuron, pyriproxyfen and spiromesifen C) at least one more insecticide selected from acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, 20 lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite, cartap hydrochloride, thiocyclam hydrogen oxalate, novaluron, buprofezin, 25 cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin with one or more inactive excipients.
30 Accordingly, in a main aspect of the present invention provides an a synergistic insecticidal composition comprising A) Afidopyropen B) at least one insecticide
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selected from diafenthiuron, pyriproxyfen and spiromesifen C) at least one more insecticide selected from acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, 5 fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite, cartap hydrochloride, thiocyclam hydrogen oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, 10 azadirechtrin, flupyrimin with one or more inactive excipients.
Accordingly, in a second aspect, the present invention provides a method of preparing the a synergistic insecticidal composition comprising A) Afidopyropen B) at least one insecticide selected from diafenthiuron, pyriproxyfen and spiromesifen 15 C) at least one more insecticide selected from acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, 20 propargite, cartap hydrochloride, thiocyclam hydrogen oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin with one or more inactive excipients. 25
Accordingly, in a third aspect, the present invention provides a method of protecting a plant propagation material, a plant, parts of a plant and/or plant organs that grow at a later point in time against pest damage by applying to the plant propagation material an insecticidal composition defined in the first aspect. 30
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DETAILED DESCRIPTION OF THE INVENTION
The present invention provides solution to all the problems mentioned above by providing the insecticidal composition.
5 The present invention provides a synergistic insecticidal composition comprising A) Afidopyropen B) at least one insecticide selected from diafenthiuron, pyriproxyfen and spiromesifen C) at least one more insecticide selected from acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, 10 thiamethoxam, sulfoxaflor, flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite, cartap hydrochloride, thiocyclam hydrogen oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, 15 indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin with one or more inactive excipients.
"Effective amounts” as mentioned herein means that amount which, when applied 20 to crops, is sufficient to kill or control insect-pest..
The term “formulation” and “composition” as used herein conveys the same meaning and can be used interchangeably.
25 The formulation or composition of the present invention can be in various physical forms, for example in the form of a Suspension Concentrate (SC), Suspo emulsion (SE), Capsule Suspension (CS), Oil Dispersion (OD), mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), Granules (Soil Applied Granules), Controlled Release Granules (CR 30 Granules), Slow release and Fast release microsphere Granules (MS Granules), Water Soluble Granules (SG), Water dispersible granule (WDG or WG), Jumbo
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ball formulation, Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP).
The formulation or composition of the present invention is preferably Suspension Concentrate (SC), Suspo emulsion (SE), Capsule Suspension (CS), Oil Dispersion 5 (OD), mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), Water Soluble Granules (SG), Water dispersible granule (WDG or WG), Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP). 10 As per one embodiment, a synergistic insecticidal composition comprising A) Afidopyropen B) at least one insecticide selected from diafenthiuron, pyriproxyfen and spiromesifen C) at least one more insecticide selected from acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, 15 thiamethoxam, sulfoxaflor, flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite, cartap hydrochloride, thiocyclam hydrogen oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, 20 indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin with one or more inactive excipients wherein active ingredients are present in concentration as described below:
25
Compound A
Compound B
Compound C
Active ingredients
Afidopyropen
diafenthiuron pyriproxyfen spiromesifen
acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor,
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flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite, cartap hydrochloride, thiocyclam hydrogen oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin
Concentration
0.1 to 30%
0.1 to 30%
0.1 to 40%
In another embodiment of the present invention the a synergistic insecticidal composition comprising A) Afidopyropen B) at least one insecticide selected from diafenthiuron, pyriproxyfen and spiromesifen C) at least one more insecticide 5 selected from acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite, 10 cartap hydrochloride, thiocyclam hydrogen oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin with one or more inactive excipients is effective for 15
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control of Insect-pests in the crops and plants selected genetically modified varieties or hybrid varieties or conventional varieties of Paddy (Oryza sativa), Cotton (Gossypium spp.), Jute (Corchorus oliotorus), Wheat (Triticum aestavum), Barley (Hordeum vulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Ragi (Eleusine coracana), Pearl millet (Pennisetum glaucum), Sugarcane (Saccharum 5 officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Castor (Ricinus communis), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram 10 (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato 15 (Solanum lycopersicun) , Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus) and Melons (Cucumis melo), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava 20 (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), 25 Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia 30 hortnesis).
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In one embodiment of the present invention, the pesticidal composition of present invention controls pests and insects belongs to the order Hemiptera, for example, rice leafhopper (Nephotettix nigropictus), rice brown plant hopper (Nilaparvata lugen), rice white backed plant hopper, Apple Mealy bug (Phenococcus aceris), bean aphid (Aphis fabae), black citrus aphid (Toxoptera aurantii), citrus black scale 5 (Saissetia oleae), cabbage aphid (Brevicoryne brassicae, Lipaphis erysimi), citrus red scale (Aonidiella aurantii), citrus mealybug (Planococcus citri), corn leaf aphid (Rhopalosiphum maidis), cotton aphid (Aphis gossypii), cotton leaf hoppers (Amrasca biguttula), cotton mealy bug (Planococcus spp. And Pseudococcus spp.), cotton stainer (Dysdercus suturellus), cotton whitefly (Bemisia tabaci), cowpea 10 aphid (Aphis crassivora), grain aphid (Sitobion avenae), golden glow aphid (Uroleucon spp.), grape mealybug (Pseudococcus maritimus), green peach aphid (Myzus persicae), greenhouse whitefly (Trialeurodes vaporariorum)spp., papaya mealy bug (Pracoccus marginatus), pea aphid (Acyrthosiphon pisum), sugarcane mealybug (Saccharicoccus sacchari), potato aphid (Myzus persicae), potato leaf 15 hopper (Empoasca fabae), cotton whitefly (Bemisia tabaci), tarnished plant bug (Lygus lineolaris), wooly apple aphid (Eriosoma lanigerum), yellow scale (Aonidiella citrine),order Lepidoptera, army worm (Mythimna unipuncta), asiatic rice borer (Chilo suppressalis), bean pod borer (Maruca vitrata), beet armyworm (Spodoptera exigua), black cutworm (Agrotis ipsilon), bollworm (Helicoverpa 20 spp.),cabbage looper (Trichoplusia ni), codling moth (Cydia pomonella), croton caterpillar (Achea janata), diamond backmoth (Plutella xylostella), cabbage worm (Pieris rapae), pink bollworm (Pectinophora gossypiella), sugarcane borer (Diatraea saccharalis), tobacco budworm (Heliothis virescens), tomato fruitworm (Helicoverpa zea), velvet bean caterpillar (Anticarsia gemmatalis), yellow stem 25 borer (SCirpophaga incertulas), spotted bollworm (Earias vittella), rice leaffolder (Cnaphalocrocis medinalis), pink stem borer (Sesamia spp.), tobacco leafeating caterpillar (Spodoptera litura), ; from the order Coleoptera, for example, apple twig borer (Amphicerus spp.), corn root worm (Diabrotica virgifera), cucumber beetle (diabrotica balteata), boll weevil (Anthonomus grandis), grape flea beetle (Altica 30 chalybea), grape root worm (Fidia viticola), grape trunk borer (Clytoleptus albofasciatus), radish flea beetle (Phyllotreta armoraciae), maize weevil (Sitophilus
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zeamais), northern corn rootworm (Diabrotica barberi), rice water weevil (Lissorhoptrus oryzophilus; from the order Orthoptera, for example, Gryllotalpa spp., Locusta spp., and Schistocerca is spp.; from the order Thysanoptera, for example, Frankliniella spp., Thrips palmi, Thrips tabaci and Scirtothrips dorsalis; from the order Heteroptera, for example, Dysdercus spp., Leptocorisa spp., from the 5 order Hymenoptera, for example, Solenopsis spp. ; from the order Diptera, for example, Antherigona soccata, Dacus spp., Liriomyza spp., Melanagromyza spp., from the order Acarina, for example, Aceria mangiferae, Brevipalpus spp., Eriophyes spp., Oligonychus mangiferus, Oligonychus punicae, Panonychus citri, Panonychus ulmi, Polyphagotarsonemus latus, Tarsonemus spp., Tetranychus 10 urticae, Tetranychus cinnabarinus.
The insecticidal composition according to the invention can be applied to any and all developmental stages of pests, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground 15 or its locus with an effective amount of the composition of present invention.
Method of Applications :
The composition of present invention can be applied by any of the below mentioned method; 20
Foliar application / spraying
Soil drenching
Through drip irrigation
Nursery bed application 25
Mixing in to soil or other plant growing media in protected cultivations, green houses, net houses, poly houses.
The term "health of a plant" or "plant health" is defined as a condition of the plant and/or its products. As a result of the improved health, yield, plant vigor, quality 30 and tolerance to abiotic or biotic stress are increased. Noteworthy, the health of a plant when applying the method according to the invention, is increased independently of the pesticidal properties of the active ingredients used because the
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increase in health is not based upon the reduced pest pressure but instead on complex physiological and metabolic reactions which result for example in an activation of the plant's own natural defense system. As a result, the health of a plant is increased even in the absence of pest pressure. Accordingly, in an especially preferred embodiment of the method according to the invention, the health of a 5 plant is increased both in the presence and absence of biotic or abiotic stress factors. The above identified indicators for the health condition of a plant may be interdependent or they may result from each other. An increase in plant vigor may for example result in an increased yield and/or tolerance to abiotic or biotic stress. One indicator for the condition of the plant is the yield. "Yield" is to be understood 10 as any plant product of economic value that is produced by the plant such as grains, fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants) or even flowers (e.g. in the case of gardening plants, ornamentals). The plant products may in addition be further utilized and/or processed after harvesting. 15 In an especially preferred embodiment of the invention, the yield of the treated plant is increased. In another preferred embodiment of the invention, the yield of the plants treated 20 according to the method of the invention, is increased synergistically. According to the present invention, "increased yield" of a plant, in particular of an agricultural, silvicultural and/or horticultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the 25 same product of the plant produced under the same conditions, but without the application of the mixture according to the invention. Increased yield can be characterized, among others, by the following improved proper-ties of the plant: increased plant weight, increased plant height, increased 30 biomass such as higher overall fresh weight (FW), increased number of flowers per plant, higher grain yield, more tillers or side shoots (branches), larger leaves,
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increased shoot growth, increased protein content, increased oil content, increased starch content, increased pigment content, increased leaf are index. A further indicator for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects such as the general visual appearance. In 5 another especially preferred embodiment of the invention, the plant vigor of the treated plant is increased. In another preferred embodiment of the invention, the plant vigor of the plants treated according to the method of the invention, is increased synergistically. Improved plant vigor can be characterized, among others, by the following improved properties of the plant: improved vitality of the plant, 10 improved plant growth, improved plant development, improved visual appearance, improved plant stand (less plant verse/lodging), improved emergence, enhanced root growth and/or more developed root system, enhanced nodulation, in particular rhizobial nodulation, bigger leaf blade, bigger size, increased plant weight, increased plant height, increased tiller number, increased number of side shoots, 15 increased number of flowers per plant, increased shoot growth, increased root growth (extensive root system), increased yield when grown on poor soils or unfavorable climate, enhanced photosynthetic activity (e.g. based on increased stomatal conductance and/or increased C02 assimilation rate), increased stomatal conductance, increased C02 assimilation rate, enhanced pigment content (e.g. 20 chlorophyll content), earlier flowering, earlier fruiting, earlier and improved germination, earlier grain maturity, improved self-defence mechanisms, improved stress tolerance and resistance of the plants against biotic and abiotic stress factors such as fungi, bacteria, viruses, insects, heat stress, cold stress, drought stress, UV stress and/or salt stress, less non-productive tillers, less dead basal leaves, less input 25 needed (such as fertilizers or water), greener leaves, complete maturation under shortened vegetation periods, less fertilizers needed, less seeds needed, easier harvesting, faster and more uniform ripening, longer shelf-life, longer panicles, delay of senescence, stronger and/or more productive tillers, better extractability of ingredients, improved quality of seeds (for being seeded in the following seasons 30 for seed production), better nitrogen uptake, improved reproduction, reduced production of ethylene and/or the inhibition of its reception by the plant.
Page 17 of 39
The improvement of the plant vigor according to the present invention particularly means that the improvement of any one or several or all of the above mentioned plant characteristics are improved independently of the pesticidal action of the mixture or active ingredients (components). 5 Another indicator for the condition of the plant is the "quality" of a plant and/or its products. In an especially preferred embodiment of the invention, the quality of the treated 10 plant is increased. In another preferred embodiment of the invention, the quality of the plants treated according to the method of the invention, is increased synergistically. 15 According to the present invention, enhanced quality means that certain plant characteristics such as the content or composition of certain ingredients are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the mixtures of the present invention. Enhanced quality can be characterized, among 20 others, by following improved properties of the plant or its product: increased nutrient content, increased protein content, increased content of fatty acids, increased metabolite content, increased carotenoid content, increased sugar content, increased amount of essential amino acids, improved nutrient composition, improved protein composition, improved composition of fatty acids, improved 25 metabolite composition, improved carotenoid composition, improved sugar composition, improved amino acids composition, improved or optimal fruit color, improved leaf color, higher storage capacity, higher process ability of the harvested products. 30 Another indicator for the condition of the plant is the plant's tolerance or resistance to biotic and/or abiotic stress factors. Biotic and abiotic stress, especially over
Page 18 of 39
longer terms, can have harmful effects on plants. Biotic stress is caused by living organisms while abiotic stress is caused for example by environmental extremes. According to the present invention, "enhanced tolerance or resistance to biotic and/or abiotic stress factors" means (1) that certain negative factors caused by biotic and/or abiotic stress are diminished in a measurable or noticeable amount as 5 compared to plants exposed to the same conditions, but without being treated with a mixture according to the invention and (2) that the negative effects are not diminished by a direct action of the mixture according to the invention on the stress factors, e.g. by its fungicidal or insecticidal action which directly destroys the microorganisms or pests, but rather by a stimulation of the plants' own defensive 10 reactions against said stress factors.
One or more inactive excipient is selected from including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to 15 as “stickers” or “binders”) and buffering agent. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or stearic barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures 20 of the two types. For wettable powder formulations, the most common dispersants are sodium lignosulphonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO 25 block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very 30 good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of
Page 19 of 39
dispersants used herein include but not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.
5 Anti-freezing agent as used herein can be selected from the group consisting of polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol.
Water-based formulations often cause foam during mixing operations in production. 10 In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, 15 the function of the anti-foam agent is to displace the surfactant from the air-water interface.
A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the 20 liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to 25 improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates and the salts thereof which are standard in agricultureor mixtures 30 thereof.
Page 20 of 39
Suspension aid in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, 5 waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof). Biocides / Microorganisms cause spoilage of formulated products. Therefore anti-10 microbial agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such as sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-15 methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxy benzoates or mixtures thereof. Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspo-emulsions to modify the rheology or flow 20 properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, 25 bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; 30 carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof. Other types
Page 21 of 39
of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.
The quick coating agent can be a conventionally available sticker, for example polyesters, polyamides, poly- carbonates, polyurea and polyurethanes, acrylate 5 polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, vinylalcohol, vinylacetate and vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymersand mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl 10 methacrylate), poly(methylmethacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, 15 poly(orthoesters), alkyd resins, and mixtures of two or more of these. Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an application environment. Examples of biodegradable polymers that are useful in the present invention include 20 biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch esteraliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, 25 biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.
Buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Potassium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium 30 phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.
Page 22 of 39
The solvent for the formulation of the present invention may include water, water-soluble alcohols and dihydroxy alcohol ethers. The water-soluble alcohol which can be used in the present invention may be lower alcohols or water-soluble macromolecular alcohols. The term "lower alcohol", as used herein, represents an 5 alcohol having 1-4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. Macromolecular alcohol is not limited, as long as it may be dissolved in water in a suitable amount range, polyethylene glycol, sorbitol, glucitol, etc. The examples of suitable dihydroxy alcohol ethers used in the present invention may be dihydroxy alcohol alkyl ethers or dihydroxy 10 alcohol aryl ethers. The examples of dihydroxy alcohol alkyl ether include ethylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, dipropylene glycol ethyl ether, etc. The examples of dihydroxy alcohol aryl ethers include ethylene glycol phenyl ether, 15 diethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, and the like. Any of the above mentioned solvent can be used either alone or in combination thereof. 20 EXAMPLES The present invention will now be explained in detail by reference to the following formulation examples and a test example, which should not be construed as limiting the scope of the present invention. 25 Example 1: Suspension Concentrate (SC) formulation of Afidopyropen 4%+Diafenthiuron 20%+Pyriproxyfen 7.5%
Chemical Composition
Percent (% w/w)
Afidopyropen a.i.
4.00
Diafenthiuron a.i.
20.00
Pyriproxyfen a.i.
7.50
Page 23 of 39
Ethoxylated Fatty Alcohol
2.00
Acrylic graft copolymer
3.00
Alkylated naphtalene sulfonate, sodium salt
0.50
Silicone antifoam
0.50
1,2-benzisothiazolin-3-one
0.20
Mono Ethylene Glycol
5.00
Xanthan powder
0.20
D.M Water
Q.S
Total
100.00 Manufacturing process of Suspension Concentrate (SC)
Step 1
Gum Solution should be made 12-18 hour prior to use. Take required quantity of water, biocide, and defoamer and homogenise, then slowly add gum powder to it and stir till complete dissolution.
Step 2
Charge required quantity of DM water need to be taken in designated vessel for Suspension concentrate production.
Step 3
Add required quantity of Wetting agent, antifreeze, dispersing agent & suspending agents and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 4
Then add technical and other remaining adjuvants excluding ‘thickener’ are added to it and homogenised to get uniform slurry ready for grinding.
Step 5
Before grinding half the quantity of antifoam was added and then material was subjected to grinding in Dyno mill till desired particle size is achieved.
Step 6
Half quantity of the antifoam was added after grinding process completes and before sampling for in process analysis.
Step 7
Finally add gum solution to this formulation and send to QC for quality check. Storage stability-Suspension Concentrate (SC) formulation of Afidopyropen 5 25%+Diafenthiuron 4%+Pyriproxyfen 10%
Laboratory storage stability for 14 days
Parameters
Specification (In house)
Initial
Stability (for 14 days)
At 54±2 0C
At 0±2 0C
Description
Off white colour flowable liquid
Complies
Complies
Complies
Afidopyropen content percent by mass
3.8 to 4.4
4.20
4.12
4.18
Diafenthiuron contnet
19.0 to 21.0
20.15
20.06
20.14
Page 24 of 39
percent by mass
Pyriproxyfen content percent by mass
7.13 to 8.25
7.59
7.53
7.58
Afidopyropen suspensibility percent mini.
80
98.15
96.01
97.65
Diafenthiuron suspensibility percent mini.
80
97.23
95.22
97.23
Pyriproxyfen suspensibility percent mini.
80
98.89
96.15
98.92
pH range (1% aq. Suspension)
5.5 to7.5
7.05
7.08
7.05
Pourability
95 % min
98.70
97.70
97.60
Specific gravity
1.05 – 1.15
1.09
1.09
1.09
Viscosity at spindle no.62, 20 rpm
350 -800 cps
460
490
495
Particle size (micron)
D50 <3, D90 <10
2.2, 7.9
2.6, 8.5
2.7, 8.5
Persistent foam ml (after 1 minute) max.
60
5
10
5 Room temperature storage data
Parameters
Specification (In house)
Study Duration
1 month
6 month
12 months
Description
Off white colour flowable liquid
Complies
Complies
Complies
Afidopyropen content percent by mass
3.8 to 4.4
4.20
4.19
4.17
Diafenthiuron contnet percent by mass
19.0 to 21.0
20.14
20.13
20.11
Pyriproxyfen content percent by mass
7.13 to 8.25
7.59
7.58
7.57
Afidopyropen suspensibility percent mini.
80
98.38
98.75
98.54
Diafenthiuron suspensibility percent mini.
80
97.75
97.68
97.15
Pyriproxyfen suspensibility percent mini.
80
98.45
98.63
98..58
pH range (1% aq. Suspension)
5.5 to7.5
7.05
7.06
7.06
Page 25 of 39
Pourability
95 % min
98.70
98.60
98.30
Specific gravity
1.05 – 1.15
1.09
1.09
1.09
Viscosity at spindle no.62, 20 rpm
350 -800 cps
460
465
470
Particle size (micron)
D50 <3, D90 <10
2.2, 8
2.2, 8.1
2.3, 8.2
Persistent foam ml (after 1 minute) max.
60
2
5
5 Example 2: Suspension Concentrate (SC) formulation of Afidopyropen 4% + Diafenthiuron 20% + Tolfenpyrad 7.5% 5
Chemical Composition
Percent (% w/w)
Afidopyropen a.i.
4.00
Diafenthiuron a.i.
20.00
Tolfenpyrad a.i.
7.50
Ethoxylated Fatty Alcohol
2.00
Acrylic graft copolymer
3.00
Alkylated naphtalene sulfonate, sodium salt
0.50
Silicone antifoam
0.50
1,2-benzisothiazolin-3-one
0.20
Mono Ethylene Glycol
5.00
Xanthan powder
0.20
D.M Water
Q.S
Total
100.00 Procedure: as per Example 1 Storage stability-Suspension Concentrate (SC) formulation of Afidopyropen 4% + Diafenthiuron 20% + Tolfenpyrad 7.5% SC 10
Laboratory storage stability for 14 days
Parameters
Specification (In house)
Initial
Stability (for 14 days)
At 54±2 0C
At 0±2 0C
Description
Off white colour flowable liquid
Complies
Complies
Complies
Afidopyropen content percent by mass
3.8 to 4.4
4.22
4.16
4.21
Page 26 of 39
Diafenthiuron contnet percent by mass
19.0 to 21.0
20.25
20.05
20.15
Tolfenpyrad content percent by mass
7.13 to 8.25
7.58
7.51
7.57
Afidopyropen suspensibility percent mini.
80
98.14
95.65
97.86
Diafenthiuron suspensibility percent mini.
80
97.85
94.17
97.55
Tolfenpyrad suspensibility percent mini.
80
97.15
93.15
96.95
pH range (1% aq. Suspension)
5.5 to7.5
7.03
7.01
7.03
Pourability
95 % min
98.70
97.70
97.60
Specific gravity
1.05 – 1.15
1.08
1.08
1.08
Viscosity at spindle no.62, 20 rpm
350 -800 cps
460
490
495
Particle size (micron)
D50 <3, D90 <10
2.2, 7.9
2.6, 8.5
2.7, 8.5
Persistent foam ml (after 1 minute) max.
60
5
10
5 Room temperature storage data
Parameters
Specification (In house)
Study Duration
1 month
6 month
12 months
Description
Off white colour flowable liquid
Complies
Complies
Complies
Afidopyropen content percent by mass
3.8 to 4.4
4.22
4.21
4.20
Diafenthiuron contnet percent by mass
19.0 to 21.0
20.24
20.23
20.22
Tolfenpyrad content percent by mass
7.13 to 8.25
7.58
7.57
7.56
Afidopyropen suspensibility percent mini.
80
97.98
97.65
97.11
Diafenthiuron suspensibility percent mini.
80
97.75
97.68
97.15
Tolfenpyrad suspensibility percent mini.
80
97.58
96.55
95.14
pH range (1% aq.
5.5 to7.5
7.03
7.03
7.01
Page 27 of 39
Suspension)
Pourability
95 % min
98.70
98.60
98.30
Specific gravity
1.05 – 1.15
1.08
1.08
1.08
Viscosity at spindle no.62, 20 rpm
350 -800 cps
460
465
470
Particle size (micron)
D50 <3, D90 <10
2.2, 8
2.2, 8.1
2.3, 8.2
Persistent foam ml (after 1 minute) max.
60
2
5
5 Example 3: Suspension Concentrate (SC) formulation of Afidopyropen 4% + Diafenthiuron 20% + Bifenthrin 5%
Chemical Composition
Percent (% w/w)
Afidopyropen a.i.
4.00
Diafenthiuron a.i
20.00
Bifenthrin a.i.
5.00
Ethoxylated Fatty Alcohol
2.00
Acrylic graft copolymer
3.00
Alkylated naphtalene sulfonate, sodium salt
0.50
Silicone antifoam
0.50
1,2-benzisothiazolin-3-one
0.20
Mono Ethylene Glycol
5.00
Xanthan powder
0.20
D.M Water
Q.S
Total
100.00 5 Procedure: as per Example 1 Example 4: Suspension Concentrate (SC) formulation of Afidopyropen 4% + Pyriproxyfen 7.5% + Tolfenpyrad 7.5%. 10
Chemical Composition
Percent (% w/w)
Afidopyropen a.i.
4.00
Pyriproxyfen a.i.
7.50
Tolfenpyrad a.i.
7.50
Ethoxylated Fatty Alcohol
2.00
Acrylic graft copolymer
3.00
Page 28 of 39
Alkylated naphtalene sulfonate, sodium salt
0.50
Silicone antifoam
0.50
1,2-benzisothiazolin-3-one
0.20
Mono Ethylene Glycol
5.00
Xanthan powder
0.30
D.M Water
Q.S
Total
100.00 Procedure: as per Example 1 Example 5: Suspension Concentrate (SC) formulation of Afidopyropen 4% + Pyriproxyfen 7.5% + Bifenthrin 5% 5
Chemical Composition
Percent (% w/w)
Afidopyropen a.i.
4.00
Pyriproxyfen a.i.
7.50
Bifenthrin a.i.
5.00
Ethoxylated Fatty Alcohol
2.00
Acrylic graft copolymer
3.00
Alkylated naphtalene sulfonate, sodium salt
0.50
Silicone antifoam
0.50
1,2-benzisothiazolin-3-one
0.20
Mono Ethylene Glycol
5.00
Xanthan powder
0.25
D.M Water
Q.S
Total
100.00
Most Preferred formulations
AI-1
AI-2
active ingredient 3
active ingredients in %
Formulation Strength (%)
Formulation Type
Application Rate (g per hectare)
g.a.i per hectare
a.i.1
a.i.2
a.i.3
a.i.1
a.i.2
a.i.3
6
AI-1
AI-2(i)
Pyriproxyfen
4
20
7.5
31.5
SC
1000
40.00
200.00
75.00
7
AI-1
AI-2(i)
Spiromesifen
4
20
7.5
31.5
SC
1000
40.00
200.00
75.00
8
AI-1
AI-2(i)
Tolfenpyrad
4
20
7.5
31.5
SC
1000
40.00
200.00
75.00
9
AI
AI-
Bifenthrin
4
20
5
29
SC
1000
40.
200
50.
Page 29 of 39
-1
2(i)
00
.00
00
10
AI-1
AI-2(i)
Lambda Cyhalothrin
4
20
5
29
SC
1000
40.00
200.00
50.00
11
AI-1
AI-2(i)
Clothianidin
4
20
7.5
31.5
WDG
1000
40.00
200.00
75.00
12
AI-1
AI-2(ii)
Spiromesifen
4
7.5
7.5
19
SC
1000
40.00
75.00
75.00
13
AI-1
AI-2(ii)
Tolfenpyrad
4
7.5
7.5
19
SC
1000
40.00
75.00
75.00
14
AI-1
AI-2(ii)
Bifenthrin
4
7.5
5
16.5
WP
1000
40.00
75.00
50.00
15
AI-1
AI-2(ii)
Lambda Cyhalothrin
4
7.5
5
16.5
SC
1000
40.00
75.00
50.00
16
AI-1
AI-2(ii)
Clothianidin
4
7.5
7.5
19
SC
1000
40.00
75.00
75.00
17
AI-1
AI-2(iii)
Tolfenpyrad
4
7.5
7.5
19
SC
1000
40.00
75.00
75.00
18
AI-1
AI-2(iii)
Bifenthrin
4
7.5
5
16.5
SC
1000
40.00
75.00
50.00
19
AI-1
AI-2(iii)
Lambda Cyhalothrin
4
7.5
5
16.5
WG
1000
40.00
75.00
50.00
20
AI-1
AI-2(iii)
Clothianidin
4
7.5
7.5
19
SC
1000
40.00
75.00
75.00 AI-1=Afidopyropen; AI-2(i)=Diafenthiuron; AI-2(ii)=Pyriproxyfen; AI-2(iii)=Spiromesifen
Biological examples 5
A synergistic effect exists wherever the action of a combination of active ingredient is greater than the sum of the action of each of the components alone. Therefore a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater pesticidal activity than the sum of the pesticidal activities of the individual components. 10
In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two active components can be calculated as 15 follows:
The % insect control data used to calculate the synergism, as per the below formula.
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The synergistic pesticide action of the inventive mixtures calculated as follows:
Field experiments of inventive synergistic mixtures of afidopyropen+diafenthiuron+pyriproxyfen, 5 afidopyropen+diafenthiuron+tolfenpyrad and afidopyropen+diafenthiuron+bifenthrin.were carried out on brinjal crop to evaluate bio-efficacy against sucking insect-pests damaging the crops.
EXPERIMENT 1: Control of Whitefly, Bemisia tabaci in brinjal crop. 10
Crop & Variety : Brinjal, Dolli
Location : Anand, Gujarat
Treatments : 16
Replication : Three
Plot size : 30 m2 (6 m x 5 m) 15
Spacing : 90 cm X 60 cm
Crop Stage at spraying: Flowering and fruiting (75 days after transplanting)
Method of Application: Foliar spray with back pack sprayer fitted with hollow cone nozzle
20
Agronomic Practices : Fertilizer, irrigation, inter culturing and weeding done as per
the crop requirement.
Observation Methods:
25
Record the number of insects (species wise) per leaf, such three leaves per plant and five plants per plot at 0, 1, 5, 10 and 15 days after application (DAA).
For whitefly, record nymph and adult together, for jassid, record nymph+adults together.
Calculate percent insect control and then calculate Colby ratio to study synergism. 30
E = X + Y + Z -- { XY + YZ + XZ } + ( X Y Z )
100 10000
Where E = Expected % control by mixture of three products A, B and C in a defined dose
X = Observed % control by product A
Y = Observed % control by product B
Z = Observed % control by product C
Ratio = Observed Control %
Expected Control %
Ratio of O/E > 1, means synergism observed.
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Table 1: Treatment composition
Treatment compositions
Formulation (ml/500 lit water)
gram active ingredient /500 lit water
Sample ABC-Afidopyropen 4%+Diafenthiuron 20%+Pyriproxyfen 7.5% SC
1000 ml
40+200+75
Sample ABD-Afidopyropen 4%+Diafenthiuron 20%+Tolfenpyrad 7.5% SC
1000 ml
40+200+75
Sample ABE-Afidopyropen 4%+Diafenthiuron 20%+Bifenthrin 5% SC
1000 ml
40+200+50
Sample AB-Afidopyropen 4%+Diafenthiuron 20% SC
1000 ml
40+200
Sample AC-Afidopyropen 4%+Pyriproxyfen 7.5% SC
1000 ml
40+75
Sample AD-Afidopyropen 4%+Tolfenpyrad 7.5% SC
1000 ml
40+75
Sample AE-Afidopyropen 4%+Bifenthrin 5% SC
1000 ml
40+50
Sample BC-Diafenthiuron 20%+Pyriproxyfen 7.5% SC
1000 ml
200+75
Sample BD-Diafenthiuron 20%+Tolfenpyrad 7.5% SC
1000 ml
200+75
Sample BE-Diafenthiuron 20%+Bifenthrin 5% SC
1000 ml
200+50
Sample A-Afidopyropen 5% DC
800 ml
40
Sample B-Diafenthiuron 50% SC
400 ml
200
Sample C-Pyriproxyfen 10% EC
750 ml
75
Sample D-Tolfenpyrad 15% EC
500 ml
75
Sample E-Bifenthrin 8% SC
625 ml
50
UTC (Untreated Check)
0
0
ml- mili liter, sc-suspension concentrate, ec-emulsifiable concentrate, dc-dispersible concentrate
Table 2: Synergistic activity against whitefly, Bemisia tabaci 5
Treatment compositions
% Whitefly Control Observed
% Whitefly Control Expected
Colby Ratio O/E
5 DAA
10 DAA
5 DAA
10 DAA
5 DAA
10 DAA
Sample ABC
99.2
98.8
89.31
88.05
1.11
1.12
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Sample ABD
98.6
97.8
90.65
87.14
1.09
1.12
Sample ABE
97.8
96.2
87.89
82.48
1.11
1.17
Sample AB
79.8
70.2
80.28
74.69
0.99
0.94
Sample AC
76.8
75.8
77.45
77.63
0.99
0.98
Sample AD
79.8
74.6
80.28
75.92
0.99
0.98
Sample AE
73.6
65.6
74.46
67.20
0.99
0.98
Sample BC
72.4
71.8
74.31
74.80
0.97
0.96
Sample BD
75.8
70.6
77.53
72.87
0.98
0.97
Sample BE
68.4
62.4
70.90
63.05
0.96
0.99
Sample A
58.4
52.6
Sample B
52.6
46.6
Sample C
45.8
52.8
Sample D
52.6
49.2
Sample E
38.6
30.8
UTC
0.0
0.0
DAA- Days after application
Field experiments shows that combination of sample afidopyropen+diafenthiuron+pyriproxyfen, afidopyropen+diafenthiuron+tolfenpyrad and afidopyropen+diafenthiuron+bifenthrin.shows synergistic activities on whitefly, 5 compared to their two active ingredient mixtures as well as solo application.
Table 3: Residual control against whitefly on brinjal crop
Treatment compositions
% Whitefly Control Observed
1 DAA
5 DAA
10 DAA
15 DAA
Sample ABC
96.4
99.2
98.8
92.40
Sample ABD
96.2
98.6
97.8
91.80
Sample ABE
98.4
97.8
96.2
91.20
Sample AB
80.6
79.8
70.2
62.60
Sample AC
72.4
76.8
75.8
65.40
Sample AD
78.4
79.8
74.6
60.40
Sample AE
72.8
73.6
65.6
61.60
Sample BC
70.6
72.4
71.8
64.20
Sample BD
74.4
75.8
70.6
58.20
Sample BE
67.2
68.4
62.4
56.80
Sample A
56.8
58.4
52.6
48.4
Sample B
50.2
52.6
46.6
40.2
Sample C
42.8
45.8
52.8
42.8
Sample D
50.8
52.6
49.2
36.6
Sample E
46.2
38.6
30.8
20.2
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UTC
0.0
0.0
0.0
0.0
Field experiments shows that combination of sample afidopyropen+diafenthiuron+pyriproxyfen, afidopyropen+diafenthiuron+tolfenpyrad and afidopyropen+diafenthiuron+bifenthrin.shows residual control of whitefly, 5 compared to their two active ingredient mixtures as well as solo application. ,CLAIMS:CLAIMS We claim; [CLAIM 1]. An synergistic insecticidal composition comprising : A) Afidopyropen; B) at least one insecticide selected from diafenthiuron, pyriproxyfen and spiromesifen; C) at least one more insecticide selected from acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite, cartap hydrochloride, thiocyclam hydrogen oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin; and D) one or more other inactive excipients. [CLAIM 2]. The synergistic composition as claimed in claim 1 wherein the component (A) Afidopyropen is in ratio of 0.1 to 30%, component (B) at least one insecticide selected from diafenthiuron, pyriproxyfen and spiromesifen is in ratio of 0.1 to 30% and component (C) at least one more insecticide selected from acephate, chlorpyrifos, profenofos, fipronil, bifenthrin, lambda cyhalothrin, fenpropathrin, acetamirprid, clothianidin, dinotefruan, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradifurone, triflumezopyrim, spinetoram, spinosad, abamectin, emamectin benzoate, fenoxycarb, pymetrozine, pyrifluquinazon, hexythiazox, etoxazole, propargite, cartap hydrochloride, thiocyclam hydrogen
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oxalate, novaluron, buprofezin, cyromazine, methoxyfenozide, tebufenozide, acequinocyl, bifenazate, fenazaquin, fenpyroximate, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spirotetramat, chlorantraniliprole, cyantraniliprole, flubendiamide, flonicamid, azadirechtrin, flupyrimin is in ratio of 0.1 to 40%. [CLAIM 3]. The synergistic composition as claimed in claim 1 or 2, wherein inactive excipients are selected from the group consisting of dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent. [CLAIM 4]. The synergistic composition as claimed in claim 1-3, wherein the formulations comprises of Suspension Concentrate (SC), Suspo emulsion (SE), Capsule Suspension (CS), Oil Dispersion (OD), mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), , Water Soluble Granules (SG), Water dispersible granule (WDG or WG), Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP). [CLAIM 5]. The formulation comprising the synergistic composition as claimed in claim 1 or 4, wherein the Suspension Concentrate (SC) formulation comprises: a) component (A) Afidopyropen is in ratio of 0.1 to 30%, component (B) at least one insecticide is in ratio of 0.1 to 30% and component (C) at least one more insecticide is in ratio of 0.1 to 40%; b) Ethoxylated Fatty Alcohol c) Acrylic graft copolymer d) Alkylated naphtalene sulfonate, sodium salt
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e) Silicone antifoam f) 1,2-benzisothiazolin-3-one g) Mono Ethylene Glycol h) Xanthan powder i) D.M Water. [CLAIM 6]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition is to be used to manage or control Insect-pests in the crops selected from genetically modified varieties or hybrid varieties or conventional varieties of Paddy Oryza sativa, Cotton Gossypium spp., Wheat Triticum aestavum, Maize Zea mays, Sugarcane Saccharum officinarum, Soybean Glycin max, Peanut Arachis hypogaea, Sunflower Helianthus annuus, Mustard Brassica juncea, Green gram Vigna radiate, Black gram Vigna mungo, Chickpea Cicer aritinum, Cowpea Vigna unguiculata, Redgram Cajanus cajan, Brinjal Solanum melongena, Cabbage Brassica oleracea var. capitata, Cauliflower Brassica oleracea var. botrytis, Okra Abelmoschus esculentus, Onion Allium cepa L., Tomato Solanum lycopersicun, Potato Solanum tuberosum, Chilly Capsicum annum, Cucumber Cucumis sativus and Melons Cucumis melo, Apple Melus domestica, Banana Musa spp., Citrus groups Citrus spp., Grape Vitis vinifera, Mango Mangifera indica, Papaya Carica papaya, Pomegranate Punica granatum, Tea Camellia sinensis, Coffea Coffea arabica, Cumin Cuminum cyminum. [CLAIM 7]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition control pests and insects from the order order Hemiptera, for example, rice leafhopper Nephotettix nigropictus, rice brown plant hopper Nilaparvata lugen, rice white backed plant hopper, Apple Mealy bug Phenococcus aceris, bean aphid Aphis fabae, black citrus aphid Toxoptera aurantii, citrus black scale Saissetia oleae, cabbage aphid Brevicoryne brassicae, Lipaphis
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erysimi, citrus red scale Aonidiella aurantii, yellow scale Aonidiella citrine, citrus mealybug Planococcus citri, corn leaf aphid Rhopalosiphum maidis, cotton aphid Aphis gossypii, cotton jassid Amrasca biguttula biguttla, cotton mealy bug Planococcus spp. And Pseudococcus spp., cotton stainer Dysdercus suturellus, cotton whitefly Bemisia tabaci, cowpea aphid Aphis crassivora, grain aphid Sitobion avenae, golden glow aphid Uroleucon spp., grape mealybug Pseudococcus maritimus, green peach aphid Myzus persicae, greenhouse whitefly Trialeurodes vaporariorum, papaya mealy bug Pracoccus marginatus, pea aphid Acyrthosiphon pisum, sugarcane mealybug Saccharicoccus sacchari, potato aphid Myzus persicae, potato leaf hopper Empoasca fabae, cotton whitefly Bemisia tabaci, tarnished plant bug Lygus lineolaris, wooly apple aphid Eriosoma lanigerum, mango hopper Amritodus atkinsoni, Idioscopus spp. ; order Lepidoptera, army worm Mythimna unipuncta, asiatic rice borer Chilo suppressalis, bean pod borer Maruca vitrata, beet armyworm Spodoptera exigua, black cutworm Agrotis ipsilon, bollworm Helicoverpa armigera , cabbage looper Trichoplusia ni, codling moth Cydia pomonella, croton caterpillar Achea janata, diamond backmoth Plutella xylostella, cabbage worm Pieris rapae, pink bollworm Pectinophora gossypiella, sugarcane borer Diatraea saccharalis, tobacco budworm Heliothis virescens, tomato fruitworm Helicoverpa zea, velvet bean caterpillar Anticarsia gemmatalis, yellow stem borer Scirpophaga incertulas, spotted bollworm Earias vittella, rice leaffolder Cnaphalocrocis medinalis, pink stem borer Sesamia spp., tobacco leafeating caterpillar Spodoptera litura; brinjal fruit and shoot borer Leucinodes orbonalis, bean pod borer Maruca vitrata, Maruca testulalis, armyworm Mythimna separata, cotton pinkbollworm Pectinophora gossypiella, citrus leafminer Phyllocnistis citrella, cabbage butterfly Pieris bras-sicae, diamond backmoth Plutella xylostella, paddy stem borer Scirpophaga excerptallis, Scirpophaga incertulas, Scirpophaga innotata, wheat
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stem borer Sesamia inferens, Sitotroga cerealella, Spilosoma obliqua, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Trichoplusia ni, Tryporyza novella, Tuta absoluta; apple twig borer Amphicerus spp., corn root worm Diabrotica virgifera, cucumber beetle diabrotica balteata, boll weevil Anthonomus grandis, grape flea beetle Altica chalybea, grape root worm Fidia viticola, grape trunk borer Clytoleptus albofasciatus, radish flea beetle Phyllotreta armoraciae, maize weevil Sitophilus zeamais, northern corn rootworm Diabrotica barberi, rice water weevil Lissorhoptrus oryzophilus, Anthonomus grandis, Bruchus lentis, Diabrotica semipunctata, Diabrotica virgifera, Dicladispa armigera, Epila-chna varivestis, various species of white grubs are Holotrichia bicolor, Holotrichia consanguinea, Holotrichia serrata, Leptinotarsa decemlineata, Phyllotreta chrysocephala, Popillia japonica etc; from the order Orthoptera, for example, Gryllotalpa spp., Locusta spp., and Schistocerca is spp.; from the order Thysanoptera, for example, Frankliniella spp., Thrips palmi, Thrips tabaci and Scirtothrips dorsalis; termites (Isoptera), e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Leucotermes flavipes, Microtermes obesi, Odontotermes obesus, Reticulitermes flavipes, Termes natalensis; from the order Heteroptera, for example, Dysdercus spp., Leptocorisa spp., from the order Hymenoptera, for example, Solenopsis spp. ; from the order Diptera, for example, Antherigona soccata, Dacus spp., Liriomyza spp., Melanagromyza spp., from the order Acarina, for example, Aceria mangiferae, Brevipalpus spp., Eriophyes spp., Oligonychus mangiferus, Oligonychus punicae, Panonychus citri, Panonychus ulmi, Polyphagotarsonemus latus, Tarsonemus spp., Tetranychus urticae, Tetranychus cinnabarinus