Insecticidal composition

Abstract

The present invention relates to a novel synergistic insecticidal composition comprising a first active ingredient as Chlorantraniliprole, a second active ingredient as Alpha-Cypermethrin and one or more agronomically salts thereof. The present invention further provides a formulation comprising active ingredients Chlorantraniliprole, Alpha-Cypermethrin and one or more agronomically acceptable excipient(s) and process for preparation thereof. The synergistic insecticidal composition is environment friendly and has application in agriculture against a broad spectrum of insect-pests and insecticidal resistance management.

Description

[0001] A NOVEL INSECTICIDAL COMPOSITION

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to a novel insecticidal composition comprising Chlorantraniliprole, Alpha Cypermethrin and salts thereof. The present invention also provides an insecticidal formulation comprising Chlorantraniliprole, Alpha-Cypermethrin or salts thereof along with acceptable agrochemical excipients. It also provides the process of preparing the said composition which is environment friendly and its application in agriculture against a broad spectrum of insect-pests and insecticidal resistance management.

[0004] BACKGROUND OF THE INVENTION

[0005] Nowadays farmers face numerous challenges when it comes to growing crops in the field. Agricultural production is constrained by a number of biotic and abiotic factors. In particular, the damage to the crops caused by insect pests is quite high in both developed and developing countries. The extent of yield loss due to pest attacks depends on upon various factors such as the type of cultivar, density of pest population, timing of the pest attack in relation to crop phenology and agricultural practices (Dhaliwal et.al, 2013). Insects can cause significant harm to crops, animals and human beings, in particular, they can damage almost all parts of plants, including roots, stems, shoots, bark, leaves, buds, and flowers at all stages of the cropping cycle (Atwal and Dhaliwal, 2015).

[0006] It has been estimated that food production needs to increase by 60% by the year 2050 to meet the increasing global demand for food (Food and Agricultural Organization of the United Nations, The State of Food and Agriculture 2019). Achieving this taiget requires not only an increase in production but also a reduction in food losses due to pests and pathogens and food waste. The global yield losses caused by crop pests and diseases are substantial with notable losses in staple food crops, for example, average losses ranging from 21.5% (10. 1 to 28.1%) in wheat, 30.3% (24.6% to 40.9%) in rice, 22.6 % (19.5% to 41.4%) in maize, 17.2% (8. 1% to 21%) in potato and 21.4% (11 to 32.4%) in soybean (S. Savaray et.al.,). The Global Burden of pathogens and pests on major food crops.Nat.Eco 1.3.430-439(2019). The total crop loss in all categories was around 32.5%. The actual losses due to various pests have been estimated at around 26-29% for Soybean, wheat, and cotton and at 30 to 40% for maize, rice and potato, respectively.

[0007] To mitigate these losses, crop protection using chemicals aims to reduce pest-related damages to acceptable levels with minimal impact on environment. Insecticides are usually chemicals that are used for killing or inhibiting the growth of pests and involve a wide range of techniques and integrated strategies. Insecticides can be applied by several methods and at various stages of the crop cycle. Pest management is a complex process involving conventional and modern Integrated Pest Management systems. By effectively controlling pests, it can lead to increased crop yield and enhanced quality of produce consequently leading to food security.

[0008] Pesticides are the chemicals used to kill the pest or suppress the growth of pests at all stages of life cycles of the pests, which attack the crop at various stages of the crop, i.e., from land preparation (soil-borne pest) to harvesting and post-harvest control measures.

[0009] A wide range of active insecticides with different modes of action are commercially available. However, these compounds may have limitations in controlling certain group of insects or pests. To address this, various combinations are being developed to get an insecticidal composition with broader spectrum, rain fastness and enhanced duration of control.. Although a lot of efforts have been taken towards developing insecticidal compositions, a need remains to ensure the storage stability of the compositions and maintaining compatibility between two or more active ingredients while achieving superior and desirable pest control benefits without affecting the plant health and produce of the main crop.

[0010] Numerous existing patents disclose various formulations and methods related to insect pest control.

[0011] WO2013149658 describes a method for controlling agricultural pests in sugarcane, emphasizing the application of non-liquid pest control formulations that do not require water. The invention encompasses a range of insecticides, including thiamethoxam, imidacloprid, and Chlorantraniliprole, applied between crop harvesting and the spreading of mulch.

[0012] CN200910069468 discloses a novel composition featuring Chlorantraniliprole combined with abamectin or emamectin benzoate, alongside other insecticides. This composition is characterized by specific mass percentages designed to maximize syneigistic effects for controlling pests in agricultural, forestry, and gardening applications.

[0013] CN101305726A discloses a pesticide composition including synergistic effective Chlorantraniliprole and Abamectins, wherein the weight proportion between the Chlorantraniliprole and the Abamectins preferably is 1:1 to 1:9, and is 1:4 more preferably.

[0014] WO2024235738A1 discloses pesticidal mixtures comprising as active compounds A) the benzamide compound of formula (I) and B) at least one further compound B selected from fipronil, lambda- cyhalothrin, bifenthrin, tefluthrin, Alpha-Cypermethrin, thiamethoxam, clothianidin, acetamiprid, imidacloprid, dinotefuran, sulfoxaflor, triflumezopyrim, spinosad, spinetoram, abamectin, indoxacarb; metaflumizone, spiropidion, spidoxamat, Chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide; dimpropyridaz, afidopyropen, and difenoconazole, prothioconazole, flutriafol, ipconazole, tebuconazole, mefentrifluconazole, triticonazole, fluoxytioconazol, metyltetraprole, azoxystrobin, trifloxystrobin, pyraclostrobin, sedaxane, penflufen, fluopyram, fluxapyroxad, pydiflumetofen, isoflucypram, cyclobutrifluram, oxathiapiprolin, fluoxapriprolin, metalaxyl, picarbutrazox, fludioxonil, thiabendazole, thiram, thiophanate -methyl; methods and use of these mixtures for combating invertebrate pests such as insects, arachnids or nematodes in and on plants, and for protecting such plants being infested with pests, especially also for protecting plant propagation material as like seeds.

[0015] WO2024121865A1 discloses a synergistic insecticidal composition comprising binary or ternary combination of; (a) one or more insecticide selected from Tolfenpyrad, Chlorantraniliprole, Cyantraniliprole, Cyclaniliprole or Flubendiamide; (b) one or more insecticide selected from class of neonicotinoids such as Fipronil, Dinotefuran, Ethiprole, Sulfoxaflor, Acetamiprid, Clothianidin, Imidacloprid, Nitenpyram, Nithiazine, Thiacloprid or Thiamethoxam; and (c) optionally one or more insecticide selected from class of pyrethroids such as Deltamethrin, Lambda-cyhalothrin, Bifenthrin, Esfenvalerate, Fenpropathrin, Fenvalerate, Tau-fluvalinate, Permethrin, Cypermethrin, Alpha- Cypermethrin or Beta-cyfluthrin; alongwith agrochemically acceptable adjuvant, for effective management of insect-pest complex on variety of crops / fruits / vegetables.

[0016] W02023095099A1 relates to a composition of Chlorantraniliprole, acetamiprid, and lambda-cyhalothrin, combined with agrochemically acceptable excipients. It emphasizes the formulation and preparation processes for achieving optimal pest control.

[0017] While the prior art discusses a range of insecticides in binary or ternary combinations, the present invention specifically relates to a synergistic insecticidal composition of Chlorantraniliprole and Alpha- Cypermethrin. The composition according to the present invention enhances pest control efficacy while ensuring stability over time. This novel composition delivers a broad-spectrum action, effectively targeting a wide range of insect pests, while requiring lower dosages compared to conventional insecticides by minimizing impact on non-target organisms, thereby promoting sustainable agricultural practices. The present invention represents a significant advancement in the field of agrochemicals, addressing the growing need for effective and environmentally friendly pest management solutions.

[0018] SUMMARY OF THE INVENTION

[0019] In an embodiment of the present invention, there is provided an insecticidal formulation comprising (a) Chlorantraniliprole as the first active ingredient; (b) Alpha-Cypermethrin as the second active ingredient and; (c) one or more agronomically acceptable excipients.

[0020] In an embodiment, the present invention provides a synergistic insecticidal composition comprising: (a) Chlorantraniliprole as a first active ingredient, in the range of 1% to 60% by weight and (b) Alpha- Cypermethrin as the second active ingredient, in the range of 1% to 50% by weight and (c) one or more agronomically acceptable excipients.

[0021] In another embodiment, there is provided a synergistic insecticidal composition, wherein Chlorantraniliprole is in the range of 10% - 20% by weight. In yet another embodiment, Alpha-Cypermethrin in the synergistic insecticidal composition is preferably in the range of 10% - 17% by weight. In another, embodiment, the weight ratio of Chlorantraniliprole to Alpha-Cypermethrin is in the range of 1:0.5 to 1:3.

[0022] In still another embodiment, one or more agronomically acceptable excipients in the insecticidal composition is / are selected from at least one dispersing agent, at least one wetting agent, at least one absorbing agent, at least one buffering agent, at least one filler, at least one surface active agent, at least one co-surface active agent, at least anti-freeze agent, at least one anti-foaming agent, at least one phase stabilizing agent, at least one diluent, at least one thickening agent, at least one biocide, at least one solvent, at least one co-solvent, at least one water soluble monomer, at least one protective colloid, at least one acidic buffer and combinations thereof.

[0023] In a further embodiment, the synergistic insecticidal composition is formulated as a pre-mix formulation.

[0024] In still another embodiment, the present invention provides an insecticidal formulation comprising of synergistic insecticidal composition, wherein the formulation is formulated as Wettable powders (WP), Emulsifiable concentrates (EC), Suspension concentrate (SC), aqueous solutions (SL), Emulsions in water (EW), Oil-in-water emulsions, Sprayable solutions or emulsions, Oil or Water-based dispersions, Suspo-emulsions (SE), water-dispersible granules (WG), Capsule suspension (CS), mixed formulation of Capsule suspension and Emulsion in water (ZW), Water-in-oil emulsions (EO), granules (GR), Oildispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), preferably WG and SC.

[0025] In yet another embodiment, the present invention provides a synergistic insecticidal composition, wherein the pre-mix formulation is a Water dispersible Granule (WG).

[0026] In another embodiment, the present invention provides a synergistic insecticidal composition, wherein the pre-mix formulation is a Suspension Concentrate (SC).

[0027] In a further embodiment, the present invention provides a synergistic pre-mix water dispersible granule (WG) formulation comprising (a) a first active ingredient as Chlorantraniliprole in the range of 11.0% - 15.0% by weight; (b) a second active ingredient as Alpha-Cypermethrin in the range of 10.0% to 14.0% by weight; and c) one or more agronomically acceptable excipients.

[0028] In still further embodiment, there is provided synergistic pre-mix water dispersible granules (WG), wherein the water dispersible granules are 0.8 - 1.2 mm in diameter.

[0029] In a yet another embodiment, there is provided a synergistic insecticide pre-mix suspension concentrate (SC) comprising (a) the first active ingredient as Chlorantraniliprole in the range of 11.0% - 15.0% by weight; (b) the second active ingredient as Alpha-Cypermethrin in the range of 10.0% - 14.0% by weight; (c) one or more agronomically acceptable excipients; (d) remaining water.

[0030] In another aspect of the present invention, there is provided a method for broad spectrum control of pests in a site, the method comprising applying the formulation comprising: (a) the synergistic insecticide composition comprising two active ingredients: (i) 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide as the first active ingredient and (ii) racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate as used herein refers to Alpha Cypermethrin as the second active ingredient and; (b) one or more agronomically acceptable excipient.

[0031] In yet another embodiment, there is provided a method of controlling pest and eliminating insects, said method comprising applying to plants, plant parts, soil, plant seed and combinations thereof, an effective amount of synergistic insecticidal composition and / or formulations.

[0032] These and other features, aspects, and advantages of the present subject matter will be better understood with reference to the following description and appended claims. This summary is provided to introduce a selection of concepts in a simplified form. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0033] DETAILED DESCRIPTION OF THE INVENTION

[0034] Those skilled in the art will be aware that the present invention is subject to variation and modifications other than those specifically described. It is to be understood that the present invention includes all such variations and modifications. The invention also includes all such steps, features, compositions, and compounds referred to or indicated in this specification, individually or collectively and any and all combinations of any or more of such steps or features.

[0035] DEFINITIONS

[0036] For convenience, before further description of the present invention, certain terms employed in the specification, and examples are delineated here. These definitions should be read in the light of the remainder of the disclosure and understood as by a person of skill in the art. The terms used herein have the meanings recognized and known to those of skill in the art, however, for convenience and completeness, particular terms and their meanings are set forth below.

[0037] The articles “a”, “an” and “the” are used to refer to one or to more than one and all combinations of one or more of the associated listed elements (i.e., to at least one) of the grammatical object of the article and may be intended to include “included” and have the plural forms as well unless the context clearly indicates otherwise.

[0038] The terms “comprise” and “comprising” are used in the inclusive, open sense, meaning that additional elements may be included. It is not intended to be constmed as “consists of only” and are open ended transitional phrases.

[0039] Throughout this specification, unless the context requires otherwise the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated element or step or group of element or steps but not the exclusion of any other element or step or group of element or steps.

[0040] The term “including” is used to mean “including but not limited to”. “Including” and “including but not limited to” are used interchangeably.

[0041] The term “fertilization” as used herein refers to the addition of any natural or synthetic material to the plant or soil or plant in order to supply nutrients to it to keep it healthy.

[0042] The term 'plants' as used herein, refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage and fruits.

[0043] The term “foliage” as used herein refers to leaves and stem of a plant.

[0044] The term “foliar spray” as used herein refers to a solution that is sprayed over the leaves of a plant or foliage.

[0045] The term “Insects” as used herein, includes all organisms in the class Insects.

[0046] The term “Insecticidal” or “Pesticidal” as used herein, refers to the ability of an insecticide to increase the mortality or inhibit growth rate of insects at all stages of its life cycle.

[0047] The term “Control” or Controlling” pests means to inhibit through toxic effect, the ability of the pests to survive, grow, feed, and / or reproduce, or to limit pest damage or loss in crop or plants.

[0048] The term “at least one anti-freeze” as used herein refers to additives meant for decreasing the freezing point of solutions. They are added to the solution in order to make it applicable in cold environments too.

[0049] The term “at least one anti-foaming agent” used herein refers to an additive that reduces or hinders the formation of foam in industrial process liquids.

[0050] The term “at least one thickening agent” used herein refers to an additive which used to increase the viscosity of a solution The thickening agent may be one or a combination of more than one. A suitable thickening agent in any individual case may be determined by one of average / ordinary skill in the art. The term “at least one biocide” as used herein refers to a chemical substance or microorganism intended to destroy, deter, render harmless, or exert a controlling elfect on any harmful organism like Mycorhizza, bacteria, fungi and the like.

[0051] The term “at least one acidic buffer” used herein refers to a solution that has pH less than 7 and contains a weak acid and one of its salts. It resists any change to pH when another acid or base is added to it.

[0052] The term “at least one carrier” used herein refers to a substance that contains other substances to carry it to its required position such as soil or roots of plants.

[0053] The term “wet milling” used herein refers to a process of grinding or crushing solid particles in order to disperse them in another liquid solution.

[0054] The term “cps” used herein refers to SI unit of viscosity which is an abbreviated form of centipoise wherein one centipoise is equal to one millipascal second.

[0055] The term “sedimentation” used herein refers to settling or depositing a substance suspended, dispersed or dissolved in another substance.

[0056] The term “EC” used herein refers to emulsifiable concentrate which is a liquid formulation containing one or more water-immiscible organic solvent and an emulsifier.

[0057] The term “emulsifier” used herein refers to surface active agents which stabilise emulsions by increasing the extent of contact between the two immiscible liquids in the emulsion.

[0058] The term “EW” used herein refers to oil in water emulsion in which water insoluble oily phase is dispersed in water.

[0059] The term “effective amount” used herein refers to the amount of the formulation that will kill the pest. The “effective amount” will vary depending on the formulation concentration, the type of plants(s) being treated, the severity of the pest infestation, the result desired, and the life stage of the pests at various stages during treatment, among other factors. Thus, it is not always possible to specify an exact “effective amount.” However, an appropriate “effective amount” in any individual case may be determined by one of ordinary / average skilled in the art.

[0060] The term 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)- lH-pyrazole-5-carboxamide as used herein refers to Chlorantraniliprole.

[0061] The term, a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate as used herein refers to Alpha Cypermethrin..

[0062] The unit “g a.i. / ha” refers to grams of active ingredient per hectare of the field / area. The term “crop fields” refers to any field for growing crops such as rice, maize, cotton, soybean, chillies, sugarcane, fruits and vegetable crops, ornamentals, and other various crops.

[0063] Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a weight range of about 1 to 300 g a.i. / ha should be interpreted to include not only the explicitly recited limits of about 1 g a.i. / ha to about 300 g a.i. / ha, but also to include sub-ranges, such as 2- 300 g a.i. / ha , 3- 300 g a.i. / ha, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 1.1 g a.i. / ha, and 299.9. 1 g a.i. / ha, for example.

[0064] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosure, the preferred methods, and materials are now described. All publications mentioned herein are incorporated herein by reference.

[0065] Chlorantraniliprole also known as 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3- chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide is a novel synthetic insecticide of class anthranilic diamide of chemicals. Chlorantraniliprole is a ryanodine receptor modulator, which regulates the release of internal calcium stores and is important in muscle contraction.

[0066] Chlorantraniliprole is the insecticide from IRAC, Group 28. Ryanodine receptor channels sustained release of calcium levels within the cytosol leading to muscle contraction, paralysis and eventual death of the organism. Chlorantraniliprole typically controls, Lepidopteran, Coleopteran, and Dipteran immature pest stages through ingestion of treated plant material or through contact. However, Chlorantraniliprole also show partial activity on adults and eggs of specific species from these insect orders through direct contact with the spray or treated plant parts. Insects exposed to Chlorantraniliprole exhibit general lethargy and muscle paralysis ultimately leading to death. Chlorantraniliprole exhibits excellent differential selectivity for insect ryanodine receptors over mammalian ryanodine receptors.

[0067] Alpha Cypermethrin (also known as Alphamethrin) is composed of the enantiomeric pair “1R cis a-S” and “IS cis a-R” at a racemic composition (also know as cis-II pair). Alpha Cypermethrin, is a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethy Icy clopropane-carboxy late. Alpha Cypermethrin is a synthetic pyrethroid and its mode of action is non-systemic with contact and stomach action. Alpha Cypermethrin is considered to be more potent and longer lasting than Cypermethrin. This acts on the pests and peripheral central nervous system in very low dosages, causing muscle spasms and inflicting paralysis, thereby leading to its inability to eat. It acts by preventing transmission of impulses along nerves, brought about by blocking the passage of sodium ions through sodium channels in nerve membranes, thus preventing action potentials passing down axons. Typically, this intoxication results in a rapid knockdown and resultant mortality.

[0068] A novel pre-mixed combination according to the present invention comprises active components belonging to the different classes of insecticides having different modes of action and different spectra of pest control i.e., - one insecticide is selected from the diamide group, Chlorantraniliprole, 3-Bromo-N-[4- chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide and another insecticide is selected from synthetic pyrethroid group, Alpha Cypermethrin, a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethy Icy clopropane-carboxy late .

[0069] However, when a combination of one or more insecticides is used, the main challenge comes in developing a formulation or composition which is stable, easy to use, safe and exhibits synergistically superior extended duration of control. The inventors of the present invention have developed a formulation that overcomes the existing and other challenges.

[0070] In an embodiment of the present invention, the composition of the present invention may be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example, wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions (EW) such as oil-in-water, sprayable solutions or emulsions, oil or water-based dispersions, suspo-emulsions (SE), water-dispersible granules (WG), mixed formulation of capsule suspension (CS) and emulsion(EW) i.e. ZW formulation, ULV formulations, microcapsules or waxes Emulsion water-in-oil (EO), Granules (GR), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), ), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), preferably WG and SC.

[0071] In an embodiment of the present invention, the composition of the present invention may be formulated as water-dispersible granule (WG) formulation comprising: (1) 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide as the first active ingredient, (2) a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylateas the second active ingredient and (3) one or more agronomically acceptable excipient selected from the group comprising of: (a) at least one dispersing agent, (b) at least one wetting agent, (c) at least one absorbing agent, (d) at least one anti-foaming agent, (e) at least one buffering agent, (f) at least one filler, and / or combinations thereof. In an embodiment of the present invention, the composition of the present invention may be formulated as an emulsifiable concentrate (EC) formulation comprising: (1) 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide as the first active ingredient (2) a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate as the second active ingredient and (3) one or more agronomically acceptable excipient selected from the group consisting of: (a) at least one solvent, (b) at least one co-solvent, (c) at least surface active agent, (d) at least one co-surface active agent, (e) at least one stabilizing agent, and / or combinations thereof.

[0072] In an embodiment of the present invention, the composition of the present invention may be formulated as a wettable powder (WP) formulation comprising: (1) 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide as the first active ingredient (2) a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate as the second active ingredient and (3) one or more agronomically acceptable excipient selected from the group consisting of: (a) at least one dispersing agent, (b) at least one wetting agent, (c) at least one absorbing agent, (d) at least one anti-foaming agent, (e) at least one buffering agent, (f) at least one filler, (g) at least one stabilizing agent, and combinations thereof.

[0073] In an embodiment of the present invention, the composition of the present invention may be formulated as an emulsion (EW) such as oil in water formulation comprising: (1) 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide as the first active ingredient, (2) a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylateas the second active ingredient and (3) one or more agronomically acceptable excipient selected from the group consisting of: (a) at least one solvent, (b) at least one surface active agent, (c) at least one co-surface active agent, (d) at least one anti-freeze agent, (e) at least one anti-foaming agent, (f) at least one stabilizing agent, (g) at least one diluent, (h) at least one thickening agent, (i) at least one biocide, and / or combinations thereof.

[0074] In an embodiment of the present invention, the composition of the present invention may be formulated as capsule suspension (CS) and / or emulsion in Water (EW), i.e., ZW formulation comprising: (1) 3-Bromo- N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5- carboxamide as the first active ingredient, (2) a racemic mixture of two isomers, (S)-a-cyano-3- phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano- 3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate as the second active ingredient and (3) one or more agronomically acceptable excipient selected from the group consisting of: (a) at least one solvent, (b) at least one co-solvent, (c) at least one surface active agent, (d) at least one co-surface active agent, (e) at least one anti-freeze agent, (f) at least one anti-foaming agent, (g) at least one phase stabilizing agent, (h) at least one diluent, (i) at least one thickening agent, (j) at least one biocide, (k) at least one oil soluble monomer, (1) at least one water-soluble monomer, (m) at least one dispersing agent, (n) at least one protective colloid, (o) at least one acidic buffer, and combinations thereof.

[0075] In an embodiment of the present invention, the composition of the present invention may be formulated as Suspension Concentrates (SC) formulation comprising: (1) 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide as the first active ingredient, (2) a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate as the second active ingredient and (3) one or more agronomically acceptable excipient selected from the group consisting of: (a) at least one dispersing agent, (b) at least one wetting agent, (c) at least one surface active agent, (d) at least one co-surface active agent, (e) at least one anti-freeze agent, (f) at least one anti-foaming agent, (g) at least one phase stabilizing agent, (h) at least one diluent, (i) at least one thickening agent, (j) at least one biocide, and combinations thereof. The weight ratio of Chlorantraniliprole to Alpha-Cypermethrin is in the range of 1:0.5 to 1:3.

[0076] In an embodiment of the present invention, the composition according to the present invention comprises 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH- pyrazole-5-carboxamide as the first active ingredient in the range of 1.0 - 60 (% w / w), a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane- carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane- carboxylate as the second active ingredient in the range of 1 - 50 (% w / w) and agronomically acceptable excipients in the range of 0.1- 80 (% w / w).

[0077] In an embodiment of the present invention, the composition according to the present invention comprises 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH- pyrazole-5 -carboxamide as the first active ingredient is preferably in the range of 10.0 - 20.0 (% w / w), more preferably in the range of 11.0 - 15.0 (% w / w), a racemic mixture of two isomers, (S)-a-cyano-3- phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano- 3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate as the second active ingredient preferably in the range of 10.0 - 17.0 (% w / w), more preferably in the range of 10.0 - 14.0 (% w / w) along with agronomically acceptable excipients preferably in the range of 10 - 80 (% w / w).

[0078] In an embodiment of the present invention, the composition according to the present invention comprises 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH- pyrazole-5-carboxamide preferably in the range of 11.0- 15(% w / w), a racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate preferably in the range oflO- 14.0 (% w / w) and agronomically acceptable excipients preferably in the range of 10 - 80 (%w / w).

[0079] In an embodiment of the present invention, the composition according to the present invention further comprises one or more agronomically acceptable excipient selected from the group consisting of: (a) at least one dispersing agent, (b) at least one wetting agent, (c) at least one absorbing agent, (d) at least one buffering agent, (e) at least one filler, (f) at least one surface active agent, (g) at least one co-surface active agent, (h) at least anti-freeze agent, (i) at least one anti-foaming agent, (j) at least one phase stabilizing agent, (k) at least one diluent, (1) at least one thickening agent, (m) at least one biocide, (n) at least one solvent, (o) at least one co-solvent, (p) at least one water soluble monomer, (q) at least one protective colloid, (r) at least one acidic buffer and combinations thereof.

[0080] In an embodiment of the present invention, the composition according to the present invention comprises-

[0081] Functional role of each excipient used in the above WG formulation and a list of each of them given below-

[0082] Dispersing agent: Styrene acrylic copolymer: Tersperse 2700, Metasperse 550S, Geropon T36

[0083] Co-dispersing agent: Naphthalene sulfonate formaldehyde condensate: Supragil MNS245, Tersperse 2020, Morwet D425, Morwet D500

[0084] Binder cum co-dispersing agent: Ligno sulfonates: Borrosperse NA, Borrosperse CA,Polyfon H,Reax 85A, Ufoxane 3 A, Polyfon F

[0085] Wetting agent: Diisopropyl / Diiso butyl naphthalene sulphonates: Supragil WP, Morwet IP, Dispersol PSSSP

[0086] De foaming agent'. Silicone defoamer: SAG 1575, SAG 1572, Dowsil AFE-3101 -

[0087] Filler and Co filler: Lactose: Lactose mono hydrate Kaolin clay: Micron GL white, Agripec B24, MLA 2 Star, Ashawhite clay

[0088] In an embodiment of the present invention, the composition according to the present invention comprises-

[0089] Functional role of each excipient used in the above SC formulation and a list of each of them given below

[0090] Dispersing agent: Mixture of Polyoxyethylene ethyl ether and polyoxyethylene / polyoxy propylene block copolymer: Antarox B600, Adox 4894, Atlas G5000, Tersperse 4894, Toximul 8320

[0091] Stabilizer cum co-dispersing agent'. Acrylic copolymer solution: Geropon DA1349, Atlox 4913, Tersperse 2500

[0092] Anti-freezing agent: Polyoxyethylene oxide block copolymer: Antarox B600, Unitop 203 Propylene glycol: As Propylene glycol De foaming agent: Silicon defoamer: SAG 1575, SAG 1672, Dowsil AFE-3101

[0093] Thickening agent: Xanthan gum: Agrhopol 23 W, Kelzan S

[0094] Biocidal agent: Proxel GXL: Proxel GXL, Nipacide BIT20

[0095] Co thickening agent: Attapulgite clay: Hydroxy gel 90T, Veegum T

[0096] Buffering agent: Citric acid Diluent: De Mineralized water or De ionised water

[0097] In an embodiment of the present invention, it is possible to include other active substances such as fungicides, pesticides, weedicides or insecticides, safeners, fertilizers, growth regulators, and / or combinations thereof in the composition or formulation according to the present invention. In another embodiment of the present invention, the composition / formulation can be used in the form of a readymade formulation or as a tank mix.

[0098] In an embodiment of the present invention, the composition / formulation as described herein can be applied to plants, plant parts, soil, plant seed, and combinations thereof.

[0099] Materials and Methods:

[0100] Field trials were conducted on various major crops at different locations. Replicated field trials on rice were carried out in Tamil Nadu, trials on Maize in Karnataka, trials on soybean in Madhya Pradesh and trials on Chillies in Andhra Pradesh covering various regions of the Country. Trials were carried out with fifteen treatments, replicated four times for recording phytotoxicity observations, while three replicates for other biometric parameters to account for reproducibility of the results. The data were statistically analysed for the purpose of comparison. The treatments were applied twice, the first spray was given when the pests reached their ETL (Economic Threshold Level) and the second spray was given at 15thday after the first application. Treatments comprising of Chlorantraniliprole: 3-Bromo-N-[4-chloro-2-methyl- 6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide and Alpha Cypermethrin: racemic mixture of two isomers, (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate as used herein were mixed in required quantity and were applied as foliar spray in the respective crops. For each treatment, the appropriate rate based on unit area of application (hectare) was calculated and measured and applied as foliar spray.

[0101] Treatments were rated and compared to Untreated Control (where water is sprayed) and the Standard Insecticide treatments for the respective crops which were commercially popular and recommended. Chlorantraniliprole 18.5% Suspension Concentrate(SC), Alpha Cypermethrin, 10% Emulsifiable Concentrate(EC), Flubendiamide, 25% Water Soluble Granules(WG) and Indoxacarb, 14.5% Suspension Concentrate(SC) are the standard benchmark formulations. These commercially recommended formulations were procured from the local markets and the required quantity of the formulation was mixed in the required amount of water and applied as foliar spray uniformly.

[0102] Overall, the combination of 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide, Chlorantraniliprole and racemic mixture of two isomers, (S)- a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate and (R)- a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate. Alpha Cypermethrin in the disclosed weight ranges is essential to have desired performance of the insecticidal composition or formulation, replacing even a single component with another component does not provide the desired effect. Also, deviating from the disclosed weight ranges does not exhibit the desired result. The examples illustrate the synergistic insecticidal composition according to the present invention. They also illustrate the formulation, comprising the insecticidal composition having two active ingredients, one or more agronomically acceptable excipient and a carrier.

[0103] Examples are provided to support the stability of the formulation. The examples also include the process for obtaining and preparing the composition and the formulation. Further included is the method of application of the formulation. Studies have been carried out in different agro-climatic conditions to see its efficacy and dose optimization in different agro climatic conditions.

[0104] Observations on method of data collection on various biometric parameters are given below.

[0105] Synergism:

[0106] A synergistic effect exists whenever the action of a combination of active ingredients 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 activity than the sum of the pesticidal activities of the individual components. Colby’s formula for calculating synergism between two active ingredients is given below:

[0107] Synergism (E) = X + Y - (XY / 100)

[0108] Where, E = Expected control by mixture or combination of Compound A and Compound B in a defined dose

[0109] X = Observed control by Compound A

[0110] Y = Observed control by Compound B

[0111] If Colby’s Ratio of E >1 means synergism observed

[0112] E<1 means antagonism observed

[0113] E=1 means simple additive effect

[0114] Higher the ratio means stronger the synergism and lower the ratio means weak synergism.

[0115] Phytotoxicity:

[0116] Phytotoxicity parameters such leaf injury, wilting, vein clearing, necrosis, epinasty and hyponasty were recorded one day before application and at 3rd, 10thand 20thday of each spray application, as per phytotoxicity scaling given below. The mean values of all the observations are represented in the tables. Table 1: Phytotoxicity evaluation scale:

[0117] Predatory population: Beneficial insects

[0118] Spiders & Coccinellids:

[0119] Spider and Cocccinellids populations / hills were recorded from ten hills selected from each plot and the average populations per hill were calculated under each treatment. Observations were monitored one day before and on 3rd, 7thand 14thday after first and second applications, respectively and the data were subjected to statistical analysis.

[0120] Observations on major rice pests recorded:

[0121] Yellow Stem borer:

[0122] Among the insect pests, yellow stem borer (YSB), Scirpophaga incertulas (Walker) is the most important and devastating insect pest of rice ecosystem, causing yield loss of up to 27-34% every year. The damage is caused by caterpillars, which bore into the stem and destroy the growing tips by feeding the internal contents with typical symptoms of drying of the central shoot known as ‘dead heart’ in the vegetative phase. When the infestation occurs at the flowering stage, the ear heads become chaffy. Data were monitored on dead hearts and White ears in one square meter of area at random by counting the number of total tiller / m2area and number of damaged tillers. Then the percentage of dead tillers (dead hearts) was calculated. Observations were recorded one day before spray and on 7thand 14thday after each spray. The total number of white ear heads was monitored, per square meter plot at the heading stage and on total number of tillers observed. The percent dead hearts and white ear heads were calculated as per the formulae given below and the data were subjected to arc sine transformed and analyzed statistical. Number of dead hearts per hill

[0123] Dead Hearts (%) = - X 100

[0124] Total number of tillers per hill

[0125] Number of white ear observed per hill

[0126] White Ears (%) = - X 100

[0127] Total number of tillers observed per hill

[0128] Leaf folder:

[0129] Leaf folder, Cnaphalocrocis medinalis (Guen.) of rice, has become a major pest in many parts of the world, particularly under Indian conditions mainly due to large-scale cultivation of high-yielding varieties and excessive use of nitrogenous fertilizer. Observations were monitored by counting the number of healthy and damaged leaves from randomly selected hills from each plot one day before application of treatments as pre-treatment observation followed on 7thand 14thday after application of each spray. The percent incidence of leaf folder was calculated as follows and the data were subjected to arc sine transformed and analyzed statistically.

[0130] Number of damaged leaves per hill

[0131] Leaf Folder Damage (%) = - X 100

[0132] Total number of healthy leaves per hill

[0133] Observations on major soybean pests recorded:

[0134] The defoliators (Spodoptera litura Fab., Thysanoplusia orichalcea Fab., Chrysodeixis acuta, walker and Helicoverpa armigera (Hubner) feed on foliage, flower and pods causing significant yield loss.

[0135] Observations on larval population of defoliators (Chrysodeixis acuta, walker) were recorded per meter row length leaving boarder rows. Influence of various treatments on the larval population was evaluated against the standard treatments and results covered in Table 13.

[0136] Observations on major pests on Chillies recorded:

[0137] Spodoptera litura and Helicoverpa armigera: Chilli is an important commercial crop which is extensively grown in India including West Bengal. The crop is infested by a number of insect pest species, among them, fruit borers like Spodoptera litura and Helicoverpa armigera are reported to occur in each season causing a huge loss of yield. In this context, the novel pre-mixed formulation developed has been tested under field conditions against these borer pests.

[0138] Two insecticidal applications have been followed out of which the first spray was given coinciding with ETL of Spodoptera litura and second spray 15 days after the first spraying. Observation on Spodeoptera litura population (larval count) was recorded from randomly selected five plants per plot of each treatment one day before first spray (pre-treatment) and 3, 7, 10 and 14 days after each application (for Treatment no. 1 to 7). Similar methodology was followed in case of Helicoverpa armigera also. The total number of healthy and damaged fruits per plant was recorded from randomly selected plants per plot of each treatment one day before the first spray and on 7 and 14 days after each spraying to calculate the per cent fruit damage caused by those pests. From this data, the per cent reduction in fruit damage over control was also calculated.

[0139] The total number of healthy and damaged fruits per plant was recorded from five randomly selected plants per treatment, one day before first application and on 7 and 14 days after each spray. From this data, the per cent reduction in fruit damage over control was also calculated by given below formula:

[0140] Number of damaged fruits

[0141] Per cent fruit damage = - X 100

[0142] Total number of fruits

[0143] Observations on major pests of Maize crop recorded:

[0144] Fall Armyworm is one of the insect pests that cause a lot of concern worldwide and in South and Southeast Asia because of the hot and humid climate. Due to the prolonged summer, South Asian nations including India, Bangladesh, Pakistan, and Sri Lanka are more susceptible to an armyworm outbreak during the fall. Fall Armyworm (FAW), a species of Spodoptera frugiperda, has decimated millions of square kilometres of maize and sorghum fields and severely damaged the livelihoods of farmers in Africa and India. The number of larvae and damaged plants were counted from ten randomly selected plants before application and on 3rd, 7thand 14thday of each application.

[0145] Infested Plants

[0146] FAW infestation (%) = - X 100

[0147] Total number of Plants and the mean Number of larvae per 5 plants were also recorded.

[0148] Yield parameters:

[0149] Yields were recorded at harvest for each of the crops and were converted to per hectare basis.

[0150] Statistical Analysis:

[0151] Data generated number of larvae / plant of Helicoverpa armigera and Spodoptera litura and number of Scirtothrips dorsalis number of spider / Coccinellids and yield parameters were subjected to square root transformation and the percentage values were subjected to angular transformation before statistical analysis.

[0152] EXAMPLE 1:

[0153] Process of preparation of formulation of the present invention (Water dispersible Granules)

[0154] The insecticide composition / formulation comprising 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide (Chlorantraniliprole) and racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate, (Alpha Cypermethrin) was prepared and this composition / formulation was then used in the preparation of the formulation.

[0155] 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH- pyrazole-5-carboxamide (Chlorantraniliprole) is available in various formulation types. However, racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate, Alpha Cypermethrinthough available in Emulsifiable Concentrate(EC), Suspension Concentrate(SC) and Wettable Powder(WP) for agricultural application, it is not available in Water Dispersible Granules type.

[0156] 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH- pyrazole-5-carboxamide when formulated as a pre-mix with racemic mixture (S)-a-cyano-3- phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano- 3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate, in a Water dispersible Granule (WG) formulation, a stable formulation was obtained.

[0157] Table 2: Chlorantraniliprole 12.5% + AlphaCypermethrin 11% WG final composition

[0158] For a WG formulation, the main performance test is suspensibility test normally done by gravimetric estimation providing an approximate indication whether the required suspensibility is maintained or not.

[0159] For this product the minimum specification of suspensibility required by gravimetric estimation is 80%.

[0160] The above formulation as in Table 2 gave initial suspensibility of 84.26% and 84.06% for Chlorantraniliprole and Alpha Cypermethrin and after AHS too analyzes as 84.37% and 83.37%.

[0161] The results indicate that the above formulation is stable formulation after subjecting it to accelerated heat storage (AHS) test. For example, the appearance of the formulation was found to be same at the ambient storage (DayO) and after AHS test at 54° C for 2 weeks.

[0162] Additionally, the active ingredient (Al) content of Chlorantraniliprole and Alpha-Cypermethrin was found to be similar before and after the AHS test at 54° C for 2 weeks. This result indicates that Chlorantraniliprole and Alpha-Cypermethrin was degraded by only 0.01% and 0.03%.

[0163] The pH of the WG formulation was also found to be similar before and after subjecting the sample to AHS test at 54° C for 2 weeks indicating that the formulation is stable. Therefore, insecticidal formulation (WG) was found to pass an active ingredient stability and suspensibility studies both on 0 day and after Accelerated Heat Storage (AHS) for two weeks at 54°C. The AHS stability data is an approximate indication that the product is stable for its actual shelf life which is normally 2 years in the marketplace.

[0164] EXAMPLE 2:

[0165] Process of preparation of formulation of the present invention (Suspension Concentrate (SC)

[0166] The insecticide composition / formulation comprising 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide (Chlorantraniliprole) and racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate, (Alpha Cypermethrin) was prepared and this composition / formulation was then used in the preparation of the formulation. Chlorantraniliprole is available both as a solo crop protection chemical tool and in combination with other insecticides. It is available in many formulation delivery systems like SC, WG, GR. But in SC combination, there are still problems like phase separation, soft and hard caking issues, product getting deposited as a cake at the bottom of the container, spray ability issues. Because of this flowability issue, the increase in particle size among many other physical stability issues happens as well. So, there is a need to develop a more stable and robust combination SC formulation of Chlorantraniliprole with the other insecticide, Alpha-Cypermethrin which is a synthetic pyrethroid.

[0167] Table 3: Chlorantraniliprole 12.5% + AlphaCypermethrin 11% SC final composition

[0168] The pre-mix formulation as given in Table 3 according to the present invention gave initial suspensibility of 85.74% and 85.11% for Chlorantraniliprole and Alpha Cypermethrin. No foam pockets in the product were observed after subjecting it to AHS test at 54°C for 2 weeks which is advantageous. The pH of the WH formulation was also found to be similar before and after subjecting the sample to AHS test at 54°C for 2 weeks indicating that the formulation is stable. Therefore, no significant changes in physical and chemical properties viz., appearance, active ingredient content, viscosity, pourability and dispersion stability on subjecting to AHS for two weeks at 54°C.

[0169] EXAMPLE 3

[0170] Process of preparation of formulation of Water dispersible Granule (WDG / WG)

[0171] The Insecticide composition / formulation comprising Chlorantraniliprole: 3-Bromo-N-[4-chloro-2-methyl- 6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide and AlphaCypermethrin: racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate as a Pre-mix Water dispersible Granules(WG) prepared by the following procedure given below:

[0172] Step 1: Process of Air jet milling the mixture of Chlorantraniliprole + Alpha Cypermethrin: 13.5 g of Chlorantraniliprole, 11.4 g of Alpha Cypermethrin, and all the excipients, except the Silicone defoamer, as per their quantities given above were added one by one in a 250 ml plastic beaker. They were mixed together using a plastic spatula to form a premix powder. This premix powder was added slowly to an Air jet mill (BMF2), a machine which is arranged to receive a compressed Air supply at 6.5 to 7.0 kg / cm2pressure. The premix powder was added slowly to the mill so as to get the grinding pressure at 3.0 to 4.0 kg / cm2pressure. Once all the pre-mix powder grinding was over, the jet milled powder was analysed using a laser diffraction particle size analyser (Malvern MS3000E). Once the specification of particle size d90 reached about 7 to 14 micron, the grinding process was confirmed to be completed. The mixture, thus, obtained was called as the Milled mixture.

[0173] Step 2: Process of Dough making:

[0174] The milled mixture obtained above was added to a dough mixture (model UPLM 400) which is similar to a sigma mixture. In a beaker, a suitable quantity of de mineralized water was weighed and stored. In another beaker, a suitable quantity of silicone defoamer was weighed and kept. In the next step, initially the defoamer was added to the water and mixed well using a glass rod. The obtained solution was added to the powder and the mixture obtained was mixed in the dough mixer jar. Through this process, a wet cake called Dough was prepared.

[0175] Step 3: Process of Extruded Granule making:

[0176] The dough was passed through a lab model Tabletop Basket extruder (model VSSE 60) with 1 mm sieve. Wet granules in noodle form were prepared using the Extruder.

[0177] Step 4: Process of Fluid Bed Drying:

[0178] The wet granules were passed through a Fluid Bed Dryer (model Unifluid Nano) and dried at temperature of 50 to 55°C for 3 minutes. After 3 minutes, the dried granules were taken out of FBD.

[0179] Step 5: Process of Sieving

[0180] The dried granules were sieved by passing through a 30 mesh and retained on a 60 mesh sieve. The dried and sieved extruded granules are about 0.8 to 1.2 mm in diameter and about 90% of the product are of 1 mm diameter. The sieved granules also called as water dispersible granules were (WG) analysed and upon meeting all the test parameters, got qualified for further application.

[0181] EXAMPLE 4

[0182] Process of making a SC (Suspension Concentrate) formulation of the premix of Chlorantraniliprole

[0183] The Insecticide composition / formulation comprising Chlorantraniliprole:3-Bromo-N-[4-chloro-2-methyl- 6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide and Alpha Cypermethrin: racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate as a Pre-mix Water dispersible Granules(WG) prepared by the following procedure given below:

[0184] Step 1: Pre mix slurry preparation:

[0185] 81.0 g of Chlorantraniliprole, 68.4 of Alpha Cypermethrin was weighed into a 1 litre beaker for a 600 ml batch size and sufficient water was added into the same beaker. The solution was kept under a Silverson mixture and agitated at 800 rpm for 5 minutes. Then one by one, all the raw materials except Xanthan gum and Proxel GXL were added while agitating the mixture at 800 to 1200 rpm. After about 40 minutes of effective agitation, resulting in “Pre-mix slurry”. Finally, the ‘pre-mix slurry’ mixture was taken for wet milling stage.

[0186] Step 2: Wet milling through a bead mill

[0187] The pre-mix slurry obtained in the previous step was passed through a horizontal agitating bead mill (0.35L Lab mill , Reliance Engineering, Mumbai) operated at 3000 rpm at 10°C. The milling was continued till the particle size of 90% of the particles (d90) became 5 - 10 microns. The particle size was measured by Laser based particle size analyser (Malvern MS3000E). The mixture obtained on wet milling was called as Suspension phase.

[0188] Step 3: Post mixing stage

[0189] The suspension phase was removed from the wet milling equipment and added to a medium shear mechanical mixer (IKA RW28). The stirring speed was kept at 300 rpm at the ambient temperature. The previously prepared 2% Xanthan gum with Proxel GXL added to this suspension phase while maintaining the agitation starting from 300 rpm and suitably increasing to about 800 to 1000 rpm. Finalizing this rpm speed depends on the product and a person skilled in the art knows how much process conditions to be kept for this process step. The final mixture obtained was called as Suspension Concentrate (SC).

[0190] EXAMPLE 5

[0191] Field trials

[0192] Details of treatments (dosages ga.i. / ha and formulation dosage / ha) for carrying out field trials over the crops like Soybean, Rice, Chillies and Maize are given in Table 4. The treatments were applied twice, the first spray was given when the pests reached their ETL (Economic Threshold Level) and the second spray was given on 15thday from the first application. The treatments were applied as a blanket foliar spray.

[0193] Table 4: Treatment regimen of Chlorantraniliprole and Alpha- Cypermethrin WG formulation

[0194] The performance of the new combination of active ingredients 3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide,

[0195] Chlorantraniliprole and racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate, Alpha Cypermethrin WG formulation was evaluated in crops like Soybean, Rice, Soybean, Chillies and Maize at different agro- climatic conditions. Experiments were carried out by taking fifteen treatments in different ratios, as described in Table 4. Observations on phytotoxicity were recorded on a scale of 0-10 for all the treatments. Observations on bio-efficacy of the treatments against the target pest for respective crops, per cent reduction and yields were recorded. Impact of treatments on beneficial insects and syneigism values were also recorded.

[0196] Further examples are provided in detail that illustrate the invention but are not intended to limit the disclosure.

[0197] 5 FIELD TRIAL -1 ON SOYBEAN:

[0198] A field trial was conducted at Dhar, Madhya Pradesh, India having black soils and was sown with variety J-335. The plot size was 10 m x 10m (100 sq.m.). The treatments were imposed as foliar spray using battery operated Knapsac sprayer fitted with hollow cone nozzle with a spray volume of 500 litres per hectare. First spray was given when the pest incidence reached the Economic Threshold Level and the 10 second spray was given 15 days after the first application.

[0199] EXAMPLE 6

[0200] Phytotoxicity studies

[0201] Phytotoxicity observations were recorded for all the treatments, before application and on 3rd, 10thand at 20thday from the first application. Notation and grading used for recording phytotoxicity are nature of 15 injury: Leaf injury (L); Wilting (W); Vein Clearing (V); Necrosis (N); Epinasty (E) and Hyponasty (H).

[0202] These gradations are as the CIB protocols on the scale of 1-10, wherein grades 1-10 denote range of percentage phytotoxicity as 1=0-10%; 2=11-20%; 3=21-30%; 4=31 to 40%; 5=40 to 50%; 6=50 to 60%; 7=60 to 70%; 8=70-80%; 9=80 to 90% and 10=90 to 100%.

[0203] Tables 5 to 10 show the observations on symptoms of Leaf injury, Wilting, Vein Clearing, Necrosis, 20 Epinasty and Hyponasty on a scale of 1 to 10 at different time intervals before and after application of the treatments. None of the treatments exhibited any phytotoxicity symptoms such as Leaf injury, Wilting, Vein Clearing, Necrosis, Epinasty and Hyponasty at any stage of the soybean crop. The results clearly indicate that the pre-mix formulation of the present invention did not exhibit any phytotoxicity symptoms even at the double dosage.

[0204] 25 Table 5: Influence of treatments for probable phytotoxicity on soybean crop if any-Leaf Injury

[0205]

[0206] *Phytotoxicity observations of Leaf injury recorded was 0% and hence graded as L=1

[0207] Table 6: Influence of treatments for probable phytotoxicity on soybean crop if any-Wilting

[0208] *Phytotoxicity observations of Wilting recorded was 0% and hence graded as W=1

[0209] Table 7: Influence of treatments for probable phytotoxicity on soybean crop if any-Vein Clearing

[0210]

[0211] *Phytotoxicity observations of Vein Clearing recorded was 0% and hence graded as V=1

[0212] Table 8: Influence of treatments for probable phytotoxicity on soybean crop if any-Necrosis:

[0213] *Phytotoxicity observations of Necrosis recorded was 0% and hence graded as N=1

[0214] Table 9: Influence of treatments for probable phytotoxicity on soybean crop if any-Epinasty

[0215]

[0216] *Phytotoxicity observations of Epinasty recorded was 0% and hence graded as E=1

[0217] Table 10: Influence of treatments for probable phytotoxicity on soybean crop if any-Hyponasty

[0218] *Phytotoxicity observations of Hyponasty recorded was 0% and hence graded as H=1

[0219] Table 11: Influence of treatments on beneficial insects on soybean crop

[0220] DBS = Days Before Spray; DAS = Days After Spray

[0221] *Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0222] Table 12: Influence of treatments on beneficial insects on soybean crop:

[0223] DBS = Days Before Spray; DAS = Days After Spray

[0224] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0225] Results of the study indicate that the novel pre-mixed formulation, at all the rates evaluated did not have any impact on the population of beneficial insects, spiders / plants and Cocinnelids / plants and these were 5 comparable to that of the untreated control plot and the standard treatments taken for the purpose of comparison (Tables 11 and 12). This clearly establishes that the Novel Premix formulation was safe to the beneficial insects. Table 13: Impact of treatments on larval population of semilooper on Soybean

[0226] DBS = Days Before Spray; DAS = Days After Spray

[0227] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0228] *Percentages: Figures in parenthesis are angular transformed values and outside are the actual values Results of the study clearly indicate that the novel Pre-mix formulation at the rates evaluated, significantly reduced the larval population of semiloopers on soybean and these treatments were significantly superior to that of the standard treatments, thus, reflecting in significantly higher per cent reduction of larval population when compared to the standard treatments (Table 13). The results of the study clearly prove that the treatments of pre-mixed formulation were superior to that of the stand- alone treatments and the standards taken for the purpose of comparison.

[0229] Table 14: Impact of treatments on Yield and Synergism of Soybean

[0230] Yields recorded under the pre-mix formulation at all the rates evaluated, recorded significantly higher yields when compared to the standard treatments taken for the purpose for comparison (Table 14). The Colby’s ratio of the pre-mix formulation was above 1.00 when compared to standard treatments varying from 0.89 to 0.95, after first application. This clearly proves that the Novel pre-mix formulation of Chlorantraniliprole(3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3- phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano- 3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate)was superior to the standard treatments and Untreated Control(Table 14) and showed good synergism.

[0231] Based on the data generated from further field trials, the syneigism ratios were calculated at 7 and 14 days following the first application. The results shows that the novel pre-mix formulation comprising Chlorantraniliprole(3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3- phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano- 3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate) exhibits pronounced synergistic effect. The yields obtained were significantly higher to standard treatments as well as the untreated control (Table 15) Table 15: Influence of treatments on Yield and Synergism of Soybean

[0232] FIELD TRIAL -2 ON RICE:

[0233] A field trial was conducted at location Tiruchirapally, Tamil Nadu, India having clayey loam soils. The plot size was 15 m x 15m (225 sq.m.). The treatments were imposed as foliar spray using battery operated Knapsac sprayer fitted with hollow cone nozzle with a spray volume of 500 litres per hectare. First spray was given when the pest incidence reached the Economic Threshold Level and the second spray was given 15 days after first application.

[0234] EXAMPLE 7:

[0235] Phytotoxicity studies All the treatments did not exhibit any phytotoxicity symptoms at all the observations recorded at all the stages of the rice crop in terms of Leaf injury, Wilting, Vein Clearing, Necrosis, Epinasty and Hyponasty. The results clearly indicate that the pre-mix formulation at all rates evaluated and even at the double dosage did not exhibit any phytotoxicity symptoms on rice crop (Tables 16 to 21) Table 16: Influence of treatments for probable phytotoxicity on Rice crop if any-Leaf Injury

[0236] *Phytotoxicity observations of Leaf injury recorded was 0% and hence graded as L=1

[0237] Table 17: Influence of treatments for probable phytotoxicity on Rice crop if any- Wilting:

[0238] *Phytotoxicity observations of Wilting recorded was 0% and hence graded as W=1

[0239] Table 18: Influence of treatments for probable phytotoxicity on Rice crop if any- Vein Clearing

[0240] *Phytotoxicity observations of Vein Clearing recorded was 0% and hence graded as V=1

[0241] Table 19: Influence of treatments for probable phytotoxicity on Rice crop if any- Necrosis

[0242] *Phytotoxicity observations of Necrosis recorded was 0% and hence graded as N=1

[0243] Table 20: Influence of treatments for probable phytotoxicity on Rice crop if any-Epinasty

[0244] *Phytotoxicity observations of Epinasty recorded was 0% and hence graded as E=1

[0245] Table 21: Influence of treatments for probable phytotoxicity on Rice crop if any-Hyponasty

[0246]

[0247] *Phytotoxicity observations of Hyponasty recorded was 0% and hence graded as H=1

[0248] Table 22: Influence of treatments on beneficial insects of rice crop

[0249] DBS = Days Before Spray; DAS = Days After Spray

[0250] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0251] Table 23: Influence of treatments on beneficial insects of rice crop

[0252] DBS = Days Before Spray; DAS = Days After Spray

[0253] * Figures in parenthesis are square root transformed valnes^ / (x+0.5) and outside are the actual values

[0254] Results of the study show that the treatments of pre-mix formulation of Chlorantraniliprole + Alpha

[0255] 5 Cypermethrin at all the rates evaluated did not have any impact on the beneficial insects and these were comparable to that of the standard treatments and untreated Control (Tables 22 and 23).

[0256] Table 24: Impact of treatments on Leaf folder damage of rice crop

[0257] DBS = Days Before Spray; DAS = Days After Spray

[0258] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0259] *Percentages: Figures in parenthesis are angular transformed values and outside are the actual values

[0260] Results of the study indicate that the treatments of pre-mix formulation at the rates evaluated were 5 significantly superior to that of the standard treatments taken for the purpose of comparison at all the observations recorded (Table 24). Results show the significant reduction in the population of Leaf folder(%). Untreated Control recorded the highest Leaf folder incidence. Based on the results of the study it can be concluded that the treatments of pre-mixed formulation were significantly superior to that of the stand-alone treatments and the standard treatments taken for the purpose of comparison. 0 Table 25: Influence of treatments on reduction of population of Yellow stem borer

[0261] DBS = Days Before Spray; DAS = Days After Spray

[0262] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0263] *Percentages: Figures in parenthesis are angular transformed values and outside are the actual values

[0264] Treatments of pre-mix formulation of Chlorantraniliprole(3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate) at all the rated tested, significantly reduced the number of dead hearts and these treatments were significantly superior to that of the standard treatments. Similar trend of results was noticed in the Number of white ear population, thus, resulting in a significant reduction in the population of dead hearts and white ears when compared to the standard treatments. The results thus clearly prove that the novel pre-mix formulation of Chlorantraniliprole and Alpha Cypermethrin was significantly superior to that of the standard treatments taken for the purpose of comparison (Table 25).

[0265] Results of the study show that there is good synergism between Chlorantraniliprole (3-Bromo-N-[4- chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5- carboxamide) and Alpha Cypermethrin (racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate) in the pre-mix formulation and the results are consistent (Table 25).

[0266] Table 26: Influence of treatments on Yield and Synergism of rice crop

[0267] Results of the study show that the there is good synergism between Chlorantraniliprole and Alpha Cypermethrin in the pre-mix formulation and the results are consistent (Table 26).

[0268] Results from additional trials were generated to further validate the synergistic ratios. The synergistic ratios were calculated at 14 days from second spray for Leaf folder and Dead hearts. The data shows that 5 the pre-mix formulation of Chlorantraniliprole(3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate) exhibits significant synergistic activity. The yields obtained with the 10 said formulation were higher than those observed with the standard treatments and the untreated control (Table 27)

[0269] Table 27: Influence of treatments on Yield and Synergism of rice crop

[0270] FIELD TRIAL -3 ON CHILLIES:

[0271] A field trial was conducted at a location in Guntur region of Andhra Pradesh, India having clayey loam soils. The variety chosen for the study was LCA 620. The crop was raised as per the package of practices of local agricultural University. The plot size was 10 m x 10m (100 sq.m.). The treatments were imposed as foliar spray using battery operated Knapsac sprayer fitted with hollow cone nozzle with a spray volume of 500 litres per hectare. First spray was given when the pest incidence reached the Economic Threshold Level and the second spray was given 15 days after first application.

[0272] EXAMPLE 8:

[0273] Phytotoxicity studies All the treatments did not exhibit any phytotoxicity symptoms at all the observations recorded at all the stages of the chilli crop in terms of Leaf injury, Wilting, Vein Clearing, Necrosis, Epinasty and Hyponasty (Tables 28 to 33). The results clearly indicate that the pre-mix formulation at all rates evaluated and even at the double dosage did not exhibit any phytotoxicity symptoms on chilli crop.

[0274] Table 28: Influence of treatments for probable phytotoxicity on Chilli crop if any-Leaf Injury

[0275] *Phytotoxicity observations of Leaf injury recorded was 0% and hence graded as L=1

[0276] Table 29: Influence of treatments for probable phytotoxicity on Chilli crop if any-Wilting

[0277] *Phytotoxicity observations of Wilting recorded was 0% and hence graded as W=1 Table 30: Influence of treatments for probable phytotoxicity on Chilli crop if any-Vein Clearing

[0278] *Phytotoxicity observations of Vein Clearing recorded was 0% and hence graded as V=

[0279] Table 31: Influence of treatments for probable phytotoxicity on Chilli crop if any-Necrosis *Phytotoxicity observations of Necrosis recorded was 0% and hence graded as N=1

[0280] Table 32: Influence of treatments for probable phytotoxicity on Chilli crop if any-Epinasty

[0281] *Phytotoxicity observations of Epinasty recorded was 0% and hence graded as E=1

[0282] Table 33: Influence of treatments for probable phytotoxicity on Chilli crop if any-Hyponasty

[0283] *Phytotoxicity observations of Hyponasty recorded was 0% and hence graded as H=1

[0284] Table 34: Influence of treatments on beneficial insects

[0285] DBS = Days Before Spray; DAS = Days After Spray * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0286] Table 35: Influence of treatments on beneficial insects

[0287] DBS = Days Before Spray; DAS = Days After Spray

[0288] * Figures in parenthesis are square root transformed valnes^ / (x+0.5) and outside are the actual values Data generated, clearly indicates that the treatment of the pre-mix formulation comprising Chlorantraniliprole(3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3- phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano- 5 3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate).at all the rates evaluated did not have any significant impact on the beneficial insects, i.e., on the population of Number of spider / plant and Number of Coccinelids / plant and there was no significant difference among the treatments and these were comparable to that of the standard treatments (Table 34 and 35).

[0289] Table 36: Influence of treatments on larval population of Helicoverpa armigera on chillies

[0290] DBS = Days Before Spray; DAS = Days After Spray

[0291] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0292] *Percentages: Figures in parenthesis are angular transformed values and outside are the actual values

[0293] Table 37: Influence of treatments on mean larval population of Spodoptera litura on chilli:

[0294] DBS= Days Before Spray; DAS = Days After Spray

[0295] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0296] *Percentages: Figures in parenthesis are angular transformed values and outside are the actual values

[0297] Treatments of pre-mix formulation of Chlorantraniliprole and Alpha Cypermethrin at all the rated tested significantly reduced the mean larval population and these treatments were significantly superior to that of the standard treatments. These results thus clearly prove that the novel pre-mix formulation of, Chlorantraniliprole(3 -Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl] - 1 -(3 -chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3- phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano- 3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate) was significantly superior to that of the standard treatments taken for the purpose of comparison (Tables 36 and 37).

[0298] Table 38: Influence of treatments on Yield and Synergism of Chilli

[0299] Results of the study show good synergism between Chlorantraniliprole and Alpha Cypermethrin in the pre-mix formulation and the results are consistent (Table 38).

[0300] Results of from additional trials were obtained to confirm the synergistic ratios. The synergistic ratios were calculated at 14 days following the second spray for Spodoptera litura and Helicoverpa armigera.

[0301] 5 The results clearly shows that the novel pre-mix formulation comprising Chlorantraniliprole(3-Bromo-N- [4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5- carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate) exhibits high synergistic activity. The yields 0 recorded with the said formulation were significantly higher in comparison to the standard treatments as well as the untreated control (see Table 39). Importantly, the consistent demonstration of synergism across multiple insect pests evidences a broad-spectrum and unexpected technical effect, thereby underscoring the inventive contribution of the present formulation.

[0302] Table 39: Influence of treatments on Yield and Synergism of Chilli FIELD TRIAL-4 ON MAIZE:

[0303] A field trial was conducted at a location in Dharwad of Karnataka, India having black cotton soils. The crop was raised as per the package of practices of local agricultural University. The plot size was 10 m x 10m (100 sq.m.). The treatments were imposed as foliar spray using battery operated Knapsac sprayer fitted with hollow cone nozzle with a spray volume of 500 litres per hectare. First spray was given when the pest incidence reached the Economic Thresh hold Level and the second spray was given 15 days after first application.

[0304] EXAMPLE 9:

[0305] Phytotoxicity studies The results clearly indicate that the pre-mix formulation at all rates evaluated and even at the double dosage did not exhibit any phytotoxicity symptoms on maize crop in terms of Leaf injury, Wilting, Vein Clearing, Necrosis, Epinasty and Hyponasty at all stages of the crop (Tables 40 to 45). These treatments were comparable to that of the standard treatments.

[0306] Table 40: Influence of treatments for probable phytotoxicity on maize crop if any-Leaf Injury *Phytotoxicity observations of Leaf injury recorded was 0% and hence graded as L=1

[0307] Table 41: Influence of treatments for probable phytotoxicity on maize crop if any-Wilting

[0308] *Phytotoxicity observations of Wilting recorded was 0% and hence graded as W=1

[0309] Table 42: Influence of treatments for probable phytotoxicity on maize crop if any-Vein Clearing

[0310] *Phytotoxicity observations of Vein Clearing recorded was 0% and hence graded as V=1 Table 43: Influence of treatments for probable phytotoxicity on maize crop if any-Necrosis

[0311] *Phytotoxicity observations of Necrosis recorded was 0% and hence graded as N=1

[0312] Table 44: Influence of treatments for probable phytotoxicity on maize crop if any-Epinasty *Phytotoxicity observations of Epinasty recorded was 0% and hence graded as E=1

[0313] Table 45: Influence of treatments for probable phytotoxicity on maize crop if any-Hyponasty

[0314] *Phytotoxicity observations of Hyponasty recorded was 0% and hence graded as H=1

[0315] Table 46: Influence of treatments on beneficial insects of maize

[0316] DBS = Days Before Spray; DAS = Days After Spray

[0317] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0318] Table 47: Influence of treatments on beneficial insects of maize

[0319] DBS = Days Before Spray; DAS = Days After Spray

[0320] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0321] Data generated, clearly indicates that the treatment of the pre-mix formulation comprising Chlorantraniliprole(3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- 5 pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3- phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano- 3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate) at all the rates evaluated did not have any significant impact on the beneficial insects, i.e., on the population of Number of spider / plant and Number of Coccinelids / plant and there was no significant difference among the 0 treatments and these were comparable to that of the standard treatments (Table 46 and 47).

[0322] Table 48: Influence of treatments on mean larval population of Spodoptera frugiperda on maize

[0323] DBS = Days Before Spray; DAS = Days After Spray

[0324] * Figures in parenthesis are square root transformed values^ / (x+0.5) and outside are the actual values

[0325] *Percentages: Figures in parenthesis are angular transformed values and outside are the actual values

[0326] Treatments of pre-mix formulation Chlorantraniliprole(3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate) at all the rated tested significantly reduced the mean larval population (Table 48), when compared to the standard treatment. These treatments were significantly superior to that of the standard treatments in terms of control.

[0327] Table 49: Influence of treatments on Yield and Synergism of maize

[0328] Results from additional trials were generated to confirm the synergism ratios. The synergism ratios were calculated at 14 days after both the first and second spray for Spodoptera frugiperd. The results clearly shows that the novel pre-mix formulation of Chlorantraniliprole(3-Bromo-N-[4-chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha 5 Cypermethrin(racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate) exhibits strong synergistic activity. The yields obtained with the said formulation were significantly higher in comparison to the standard treatments and the untreated control (Table 50). Furthermore, the consistent demonstration of synergism against Spodoptera frugiperda, in 0 addition to other major pests, evidences a broad-spectrum and unexpected technical effect, thereby reinforcing the inventive merit of the present formulation.

[0329] Table 50: Influence of treatments on Yield and Synergism of maize

[0330]

[0331] Results of the study show that there is good synergism between Chlorantraniliprole(3-Bromo-N-[4- chloro-2-methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5- carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2- dichlorovinyl)- 2,2-dimethylcyclopropane-carboxylate) in the pre-mix formulation and the results are consistent.

[0332] Based on the results of the studies carried out on the major crops like Soybean, Rice, Chillies and Maize, it can be concluded that the novel pre-mixed formulation of Chlorantraniliprole(3-Bromo-N-[4-chloro-2- methyl-6- (methyl carbamoyl)phenyl]-l-(3-chloro-2- pyridine-2-yl)-lH-pyrazole-5-carboxamide) and Alpha Cypermethrin(racemic mixture (S)-a-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate and (R)-a-cyano-3-phenoxybenzyl-(lS,3S)-3-(2,2-dichlorovinyl)- 2,2- dimethylcyclopropane-carboxylate) did not exhibit any phytotoxicity to the crops, at all stages of growth and did not impact the beneficial insects and hence safe to the beneficial insects. The novel combination based on the Colby’s ratio showed good synergism. The novel pre-mixed formulation gave effective control of the pests in the respective crops and these treatments were significantly superior to the stand alone treatment and that of the standard treatments.

Claims

1. Claims:

1. A synergistic insecticidal composition comprising: a) Chlorantraniliprole as a first active ingredient in the range of 1% - 60% by weight; b) Alpha-Cypermethrin as a second active ingredient in the range of 1% - 50% by weight; and c) one or more agronomically acceptable excipients.

2. The synergistic insecticidal composition as claimed in claim 1, wherein Chlorantraniliprole is in the range of 10% - 20%, more preferably in the range of 11% - 15% by weight.

3. The synergistic insecticidal composition as claimed in claim 1, wherein Alpha-Cypermethrin is in the range of 10% - 17%, more preferably in the range of 10% - 14% by weight.

4. The synergistic insecticidal composition as claimed in claim 1, wherein the weight ratio of Chlorantraniliprole to Alpha-Cypermethrin is in the range of 1:0.5 to 1:3.

5. The synergistic insecticidal composition as claimed in claim 1 wherein, one or more agronomically acceptable excipients is / are selected from at least one dispersing agent, at least one wetting agent, at least one absorbing agent, at least one buffering agent, at least one filler, at least one surface active agent, at least one co-surface active agent, at least anti-freeze agent, at least one anti-foaming agent, at least one phase stabilizing agent, at least one diluent, at least one thickening agent, at least one biocide, at least one solvent, at least one co-solvent, at least one water soluble monomer, at least one protective colloid, at least one acidic buffer and combinations thereof.

6. The synergistic insecticidal composition as claimed in claim 1, wherein the said composition is formulated as a pre-mix formulation.

7. The synergistic insecticidal composition as claimed in claim 6 wherein, the pre-mix formulation for insecticide composition is selected from Wettable powders (WP), Emulsifiable concentrates (EC), Suspension concentrate (SC), aqueous solutions (SL), Emulsions in water (EW), Oil-in- water emulsions, Sprayable solutions or emulsions, Oil or Water-based dispersions, Suspo- emulsions (SE), water-dispersible granules (WG), Capsule suspension (CS), mixed formulation of Capsule suspension and Emulsion in water (ZW), Water-in-oil emulsions (EO), granules (GR), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), preferably WG and SC.

8. The synergistic insecticidal composition as claimed in claim 7, wherein the pre-mix formulation is a Water dispersible Granule (WG).

9. The synergistic insecticide composition as claimed in claim 7, wherein the pre-mix formulation is a Suspension Concentrate (SC).

10. A synergistic pre-mix water dispersible granule (WG) formulation comprising: a) a first active ingredient as Chlorantraniliprole in the range of 11.0% - 15.0 % by weight; b) a second active ingredient as Alpha-Cypermethrin in the range of 10.0% - 14.0% by weight; c) one or more agronomically acceptable excipients.

11. The synergistic pre-mix water dispersible granules (WG) as claimed in claim 10, wherein the water dispersible granules are 0.8 - 1.2 mm in diameter.

12. A synergistic insecticide pre-mix suspension concentrate (SC) comprising: a) the first active ingredient as Chlorantraniliprole in the range of 11.0% - 15.0% by weight; b) the second active ingredient as Alpha-Cypermethrin in the range of 10.0 % - 14.0 % by weight; c) one or more agronomically acceptable excipients; d) balance water.

13. A method of controlling pest and eliminating insects, said method comprising applying to plants, plant parts, soil, plant seed and combinations thereof, an effective amount of synergistic insecticidal composition and / or formulations as claimed in any of the preceding claims.

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