DESC:FIELD OF THE INVENTION:

The present invention relates toasynergistic insecticidal composition comprising Tolfenpyrad and an insecticide selected from Acephate, Chlorpyrifos, Pymetrozine, Flonicamid and Fenpyroximate. The present invention also relates to process for preparing the said composition comprising of bioactive amounts of Tolfenpyrad and an insecticide along with one or more inactive excipients.

BACKGROUND OF THE INVENTION

Insecticides can be classified by many ways. One of many classifications is as below:

Systemic insecticides are those in which the active ingredient is taken up, primarily by plant roots, and transported (translocated) to locations throughout the plant, such as growing points, where it can affect plant-feeding pests. Systemic insecticides move within the vascular tissues, either through the xylem (water-conducting tissue) or the phloem (food-conducting tissue) depending on the characteristics of the material.

Contact insecticides are toxic to insects when brought into direct contact. Efficacy is often related to the quality of pesticide application, with small droplets (such as aerosols) often improving performance.

Natural insecticides, such as nicotine, pyrethrum and neem extracts are made by plants as defenses against insects. Nicotine-based insecticides are widely used in the US and Canada, but are barred in the European Union.

Plant-incorporated protectants(PIPs) are systemic insecticides produced by transgenic plants. For instance, a gene that codes for a specific Bacillusthuringiensisbiocidal protein was introduced into corn and other species. The plant manufactures the protein which kills the insect when consumed.

Inorganic insecticides are contact insecticides that manufactured with metals and include arsenates, copper and fluorine compounds, which are now seldom used, and sulfur, which is commonly used.

Organic insecticides are contact insecticides that comprise the largest numbers of pesticides available for use today.

The mode of action describes how the pesticide kills or inactivates a pest. It provides another way of classifying insecticides. Mode of action is important in understanding whether an insecticide will be toxic to unrelated species, such as fish, birds and mammals.

Insecticidal classes which covers majority of the insecticides are as below:

Organophosphates and carbamates
Organophosphates target the insect's nervous system. Organophosphates interfere with the enzymes acetylcholinesterase and other cholinesterases, disrupting nerve impulses and killing or disabling the insect. Organophosphate insecticides and chemical warfare nerve agents (such as sarin, tabun, soman, and VX) work in the same way. Organophosphates have a cumulative toxic effect to wildlife, so multiple exposures to the chemicals amplify the toxicity.

Carbamate insecticides have similar mechanisms to organophosphates, but have a much shorter duration of action and are somewhat less toxic.

Organochlorides
The best-known organochloride, DDT (Dichlorodiphenyltrichloroethane), was created by Swiss scientist Paul Müller. For this discovery, he was awarded the 1948 Nobel Prize for Physiology or Medicine. DDT was introduced in 1944. It functions by opening sodium channels in the insect's nerve cells. The contemporaneous rise of the chemical industry facilitated large-scale production of DDT and related chlorinated hydrocarbons.

Neonicotinoids
Neonicotinoids are synthetic analogues of the natural insecticide nicotine (with much lower acute mammalian toxicity and greater field persistence). These chemicals are acetylcholine receptor agonists. They are broad-spectrum systemic insecticides, with rapid action (minutes-hours). They are applied as sprays, drenches, seed and soil treatments. Treated insects exhibit leg tremors, rapid wing motion, stylet withdrawal (aphids), disoriented movement, paralysis and death. Imidacloprid may be the most common.

Pyrethroids
Pyrethroid pesticides mimic the insecticidal activity of the natural compound pyrethrum. These compounds are nonpersistent sodium channel modulators and are less toxic than organophosphates and carbamates. Compounds in this group are often applied against household pests.

Ryanoids
Ryanoids are synthetic analogues with the same mode of action as ryanodine, a naturally occurring insecticide extracted from Ryaniaspeciosa (Flacourtiaceae). They bind to calcium channels in cardiac and skeletal muscle, blocking nerve transmission.

Plant-incorporated protectants
Transgenic crops that act as insecticides began in 1996 with Bt corn that produces the Cry protein, derived from the bacterium Bacillus thuringiensis, which is toxic to moth larvae such as the European corn borer. The technique has been expanded to include the use of RNA interference RNAi that fatally silences crucial insect genes. RNAi likely evolved as a defense against viruses. Midgut cells in many larvae take up the molecules and help spread the signal. The technology can target only insects that have the silenced sequence, as was demonstrated when a particular RNAi affected only one of four fruit fly species. The technique is expected to replace many other insecticides, which are losing effectiveness due to the spread of pesticide resistance.

Tolfenpyrad was first disclosed in US5039693.Tolfenpyrad is chemically known as 4-chloro-3-ethyl-1-methyl-N-[4-(p-tolyloxy)benzyl]pyrazole-5-carboxamideand having chemical structure as below;

Tolfenpyrad is a pyrazole insecticide, and was discovered by Mitsubishi Chemical Corporation in 1991. The compound acts mainly through the inhibition of the mitochondrial electron transport system

Tolfenpyrad acts by poisoning by ingestion, contact activity, anti-feeding activity against leps. Targeted crops of Tolfenpyrad include vegetable, cucurbits, cole crops, fruits and nuts, selected row crops and ornamentals. Tolfenpyrad is effective against disease including hemiptera, coleoptera, dipteral, lepidoptera, thysanoptera, orthoptera and acarina.

Acephate was first disclosed in US 2908605. IUPAC name of Acephate is N-(Methoxy-methylsulfanylphosphoryl) acetamide and chemical structure is as below;

Acephate is sold as a soluble powder, as emulsifiable concentrates, as pressurized aerosol, and in tree injection systems and granular formulations.

Acephate can kill target insects when they touch it or eat it. When insects eat Acephate, their bodies turn it into a chemical called methamidophos, which is another, stronger insecticide. Acephate is less toxic in mammals because mammal bodies do not turn it into methamidophos very well. Acephate and methamidophos affect the nervous system, causing over-activity in the nerves, muscles, or brain. Acephate is absorbed into plants, so insects that feed on treated plants may eat Acephate.

Chlorpyrifos was first disclosed in US 2758115 and have IUPAC name: O, O-diethyl O-3, 5, 6-trichloropyridin-2-yl phosphorothioate) is a crystalline organophosphate insecticide. Chemical structure of the same is as below:

Chlorpyrifos was introduced in 1965 by Dow Chemical Company and is known by many trade names including Dursban® and Lorsban®. It acts on the nervous system of insects by inhibiting acetyl cholinesterase. Chlorpyrifos works by blocking an enzyme which controls messages that travel between nerve cells. When the enzyme is blocked, the nervous system can't send normal signals. This causes the nervous system to malfunction and this is how it eventually kills the pest.

Pymetrozine was first disclosed in US4931439 and US4996325.Pymetrozine is chemically known as (E)-4,5-dihydro-6-methyl-4-(3-pyridylmethyleneamino)-1,2,4-triazin-3(2H)-one and having chemical structure as below;

The mode of action of pymetrozine in insects has not been precisely determined biochemically, but it may involve effects on neuroregulation or nerve-muscle interaction. Physiologically, it appears to act by preventing these insects from inserting their stylus in to the plant tissue.

Flonicamid was first disclosed in US5360806. Flonicamid (IKI220; N-cyanomethyl-4-trifluoromethylnicotinamide), a pyridine carboxamide compound, is a novel systemic insecticide with selective activity against hemipterous pests, such as aphids and whiteflies, and thysanopterous pests. Chemically known as N-(Cyanomethyl)-4-(trifluoromethyl)-3-pyridinecarboxamide and having chemical structure as below;

Fenpyroximate was first disclosed in EP234045.Fenpyroximate is chemically known as tert-butyl(E)-a-(1,3-dimethyl-5-phenoxypyrazol-4-ylmethyleneaminooxy)-p-toluateand having chemical structure as below;

Fenpyroximate is from phenoxypyrazole class of insecticide and is used against a wide range of phytophagous mites. It has a novel chemical structure, and has been proven effective against most phytophagous (plant-eating) mites on various crops worldwide. Fenpyroximate has quick action or knock down activity on active stages with long lasting effect. It has molting inhibition on immature stages.

The main concern with the use of pesticide is the development of resistance by the pests for that particular pesticide and at the end one has to apply more concentrated formulation of the pesticide. The high amount of pesticide may results in the toxicity to human beings as well as has bad effect on environment.

Previously people have tried many alternatives and option to overcome this problem and as a result developed poly mixture of pesticide, use of non-toxic ingredients and developing novel formulations which provides effective amount of the pesticide and at the required part only.

However the use of poly mixture containing large number of pesticides poses a problem in many was like preparing formulation of multiple pesticides with different chemical properties and behavior and physical properties. It also creates challenge for formulator in term of compatibility and stability of all the pesticide along with used excipients in the formulation.

WO2013/002299 discloses an agricultural and horticultural insecticide composition containing flubendiamide and Tolfenpyrad as active ingredients and a utilization method therefore characterized in that insects or plants infested with the insects or the surrounding land or cultivation carriers where the plants are grown are treated with an effective dose of the agricultural and horticultural insecticide composition containing flubendiamide and Tolfenpyrad as active ingredients.

CN103621532 discloses a synergistic insecticidal composition containing thiamethoxam and tolfenpyrad and application thereof. The synergistic insecticidal composition comprises main effective components of thiamethoxam and tolfenpyrad as synergistic in a weight ratio of 1-60:1-70. The insecticidal composition has expanded spectrum of control and synergistic effect, and can reduce the cost of medication, be formulated into miscible oil, wettable powder, microemulsion, aqueous emulsion, suspending agent and water dispersible granule for the control of various insects of Lepidoptera, Hemiptera, Hymenoptera and Coleoptera.

CN103621541 discloses a synergistic insecticidal composition containing clothianidin and tolfenpyrad and applications thereof. The synergistic insecticidal composition employs clothianidin and tolfenpyrad as main effective components, wherein, the weight ratio of clothianidin to tolfenpyrad is 0.1-60:0.1-50. The composition can enlarge the control spectrum, has synergistic effects, and can lower drug cost. The composition can be prepared into missible oil, wettable powder, microemulsion, emulsion in water, suspending agents and water dispersion granules, and is used for control of various insects of lepidoptera, hemiptera, hymenoptera, coleopteran and the like.

CN103053596 discloses a synergistic insecticidal composition containing tolfenpyrad and cypermethrin and an application, the synergistic insecticidal composition takes tolfenpyrad and cypermethrin as main effective components, wherein the weight ratio of tolfenpyrad to cypermethrin is 0.1-80:0.5-80. The insecticidal composition has effects for enlarging the prevention and cure scope and synergia, and the medication cost is reduced, and the synergistic insecticidal composition can be prepared to a miscible oil, a wettable powder, a microemulsion, an emulsion in water, a suspending agent and a water dispersible granule, and the synergistic insecticidal composition can be used for preventing and treating various pests such as Lepidoptera, Homoptera, Hymenoptera and coleopteran.

CN103271051 describes a tolfenpyrad-diafenthiuron composite insecticide composition having synergy. The tolfenpyrad-diafenthiuron composite insecticide composition having synergism comprises two active ingredients such as tolfenpyrad and diafenthiuron and also comprises auxiliary agents or carriers. A mass ratio of tolfenpyrad to diafenthiuron in the composite insecticide composition is in a range of 30: 1 to 1: 30. The mass of tolfenpyrad and diafenthiuron is 5 to 80% of the total mass of the tolfenpyrad-diafenthiuron composite insecticide composition. Tolfenpyrad and diafenthiuron can produce high synergism. Through the combination of tolfenpyrad and diafenthiuron, insecticide resistance of insects are reduced and delayed and environmental friendliness is obtained. The tolfenpyrad-diafenthiuron composite insecticide composition can efficiently prevent and control lepidoptera, thysanoptera and homoptera insects on vegetables, fruit trees, flowers and field crops, and is especially suitable for preventing and controlling diamondback moth, thrip and tea lesser leafhopper.

However still there is a need for a composition of Tolfenpyrad in combination with one more insecticide which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.

Inventors of the present invention have surprisingly found that the novel synergistic composition of Tolfenpyrad and an insecticide as described herein in can provide solution to the above mentioned problems.

SUMMARY OF THE INVENTION

The present invention relates to a synergistic insecticidal composition which comprises of bioactive amounts of Tolfenpyrad and an insecticide selected from Acephate, Chlorpyrifos, Pymetrozine, Flonicamid and Fenpyroximate with one or more inactive excipients.

Further the present invention also relates to process for preparing synergistic insecticidal composition comprising bioactive amounts of Tolfenpyrad and one more insecticide with one or more inactive excipients.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a novel synergistic composition comprising bioactive amounts of Tolfenpyrad and an insecticide along with one or more inactive excipients. The said insecticide is selected from Acephate, Chlorpyrifos, Pymetrozine, Flonicamid and Fenpyroximate.

"Bioactive amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficient to effect such treatment.

The insecticidal and/or fungicidal formulation can be classified as below:
a) Dry - Sprayable
a.1) WP – Wettable powders:
A solid pesticide formulation – micronized to powder form and typically applied as suspended particles after dispersion in water.
a.2) WG or WDG – Water dispersible granule:
A pesticidal formulation consisting of granules to be applied after disintegration and dispersion in water. Water dispersible granules can be formed by a) agglomeration, b) spray drying, or c) extrusion techniques. It can also be termed as water soluble granules (WSG) or soluble granules (SG).
b) Liquid Sprayable
b.1) SL – Soluble Concentrate:
A soluble concentrate is in powder form intended for dilution with water or directly in solution from. In both the case, the end result will be clear solution of the insecticide in the water without any visible un-dissolved particles.
b.2) SC – Suspension Concentrate
A stable suspension of solid pesticide(s) in a fluid usually intended for dilution with water before use. For a good formulation or ideal SC formulation, it should be stable and do not sediment over time.
b.3) EC – Emulsifiable Concentrate
A solution of a pesticide with emulsifying agents in a water insoluble organic solvent which will form an emulsion when added to water. In most of the case it is oil in water type emulsion to make it easy for application. EC formulation should be storage stable without any visible cracking of emulsion.

b.4) ME – Microemulsion
A solution of a pesticide with emulsifying agents in a water insoluble organic solvent which will form a solution/emulsion when added to water. The difference between EC and ME is the particle size of the actives in the final form.

b.5) OD – Oil Dispersion
Oil dispersions (OD) are one type of liquid formulation which is stable suspensions of active ingredients in a water-immiscible fluid which may contain other dissolved active ingredients and is intended for dilution with water before use.

b.6) CS – Capsule Suspension
Suspension of micro-encapsulated active ingredient in an aqueous continuous phase, intended for dilution with water before use.
b.7) SE- Suspension emulsion
A suspension emulsion or suspo emulsion (SE) consists of an organic phase with a dissolved active ingredient and an aqueous suspension phase, in which the active ingredient is dispersed in water.
b.8) Dispersible concentrate (DC)
Dispersible concentrate (DC) is a liquid homogeneous formulation to be applied as a solid dispersion after dilution in water. There are many formulations which contains the part characteristics of EC and part characteristics of DC.
c) Dry – Spreadable Granule
Dry spreadable granules are dry granules which can be applied with a dry spreader to a target area and later when such granules get exposed to water via, for example, rain or irrigation, will not only readily disintegrate, but actively spread on solid substrates so as to achieve disintegration area diameter to original granule diameter ratios.

Dry spreadable granules should possess good hardness and an ability to maintain integrity upon normal, commercial handling in a dry spreading operation and yet be capable of quickly disintegrating or scattering upon what may be a minimal exposure to water, such as, for example, a light rain.
d) GR – Soil applied Granule on inert or fertilizer carrier
This formulation is in the form of granules which can be applied on inert carrier or the carrier which is fertilizer.
e) Mixed formulation
e.1) ZC Formulation (Mix of CS and SC)
“ZC formulation” is the international denominations adopted by the FAO (Food and Agricultural Organization of the United Nations) to designate "stable aqueous suspension of microcapsules and solid fine particles". ZC is a mixed formulation of CS and SC and is a stable aqueous suspension of microcapsules and solid fine particles, each of which contains one or more active ingredients. The formulation is intended for dilution into water prior to spray application. Formulating the active ingredients together eliminates the need for tank mixing, which can lead to incompatibility, and facilitates control of a wider range of pests with fewer applications. Like other aqueous liquid formulations, ZC formulations are easy to handle and measure, dust free, non-flammable and offer good miscibility with water.

One or more of the active ingredients is encapsulated for various purposes, such as to increase the residual biological activity, or to reduce the acute toxicity, or to obtain a physical or chemically stable water-based formulation. The purpose determines whether the “free” active ingredient and the “release rate” are relevant properties of a specific product.

The term WDG, DG, WSG and SG are synonyms and can be used inter changeably and convey the same meaning.

Formulation of the present invention can be in any of the form described above.

Tolfenpyrad and one more insecticide selected from Acephate, Chlorpyrifos, Pymetrozine, Flonicamid and Fenpyroximate which are bio active ingredient for the present composition are present in ratio of 1:10 to 10:1.

The composition of the present invention is effective for management of insect or pests in Genetically Modified Organism (GMO) and Non GMO of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticumaestavum), Barley (Hordeumvulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Sugarcane (Saccharumofficinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachishypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linumusitatissimum), Sesame (Sesamumindicum), Castor (Ricinuscommunis), Green gram (Vigna radiate), Black gram (Vignamungo), Chickpea (Ciceraritinum), Cowpea (Vignaunguiculata), Redgram (Cajanuscajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotylomauniflorum), Field pea (Pisumsativum), Cluster bean (Cyamopsistetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanumlycopersicun) , Potato (Solanumtuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumissativus), Muskmelons (Cucumismelo), Watermelon (Citrulluslanatus), Bottle gourd (Lagenariasiceraria), Bitter gourd (Momordicacharantia), Radish (Raphanussativus), Carrot (Dacuscarota subsp. sativus), Turnip (Brassica rapasubsprapa), Apple (Melusdomestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitisvinifera), Guava (Psidiumguajava), Litchi (Litchi chinensis), Mango (Mangiferaindica), Papaya (Carica papaya), Pineapple (Ananascomosus), Pomegranate (Punicagranatum) , Sapota (Manilkarazapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiberofficinale), Cumin (Cuminumcyminum), Fenugreek (Trigonellafoenum-graecum), Fennel (Foeniculumvulgare), Coriander (Coriandrumsativum), Ajwain (Trachyspermumammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safedmusli (Chlorophytumtuberosum), Drum stick (Moringaoleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellisperennis), Dahlia (Dahlia hortnesis), Gerbera ( Gerbera jamesonii), Carnation (Dianthus caryophyllus).

The composition of the present invention can be used to control the insects-pests belongs to Lepidopteran insects, Chilopartellus, Chilosuppressalis, Cydiapomonella, Plutellaxylostella, Peirisrapae, beetles (coleopteran), e.g. Dicladispaarmigera, Phyllotretanemorum, Phyllotretastriolata, flies (Diptera), e.g. Atherigonaorientalis, Dacuscucurbi-tae, Dacusoleae, Liriomyzasativae, Liriomyzatrifolii, Melanagromyza obtuse, Ophiomyiaphaseli, thrips (Thysanoptera), e.g. Frankliniellaoccidentalis, Scirtothripscitri, Scirtothrips dorsalis, Thrips oryzae, Thrips palmi and Thrips tabaci, true bugs (Hemiptera), e.g. Amrascabiguttulabiguttula, Amrascadevastans, Amritodusatkinsoni, Aphis fabae, Aphis pomi, Aphis gossypii, Aphis crassivora, Bemisiaargentifolii, Bemisiatabaci, Brevicorynebrassicae, Clavigrallagibbosa, Dysdercuscingulatus, Idioscopus spp., Leptocorisaacuta, Lyguslineolaris, Myzuspersicae, Nilaparvatalugens, Nephotettixvirescens, Nephotettixnigropictus, Planococcus spp., Pseudococcus spp., Pyrillaperpusilla, Psylla mail, Psyllapiri, Rhopalomyzusascalonicus, Rhopalosiphummaidis, Rhopalosi-phumpadi, Rhopalosiphuminsertum, Sappaphis mala, Sappaphis mail, Schizaphisgraminum, Schizoneuralanuginosa, Sitobionavenae, Sogatellafurcifera, Trialeurodesvaporariorum, Toxopteraaurantiia, Psylla spp., Rhopalosiphum spp., Sitobion spp., crickets, grasshoppers, locusts (Orthoptera), e.g. Gryllotalpagryllo-talpa, Locustamigratoria, Melanoplusbivittatus, Locustanapardalina., from the order Acarina, for example, Brevipalpus spp., Eriophyes spp., Olygonychuscoffeae, Panonychus spp., Polyphagotarsonemuslatus, Tarsonemus spp. and Tetranychus spp. (Tetranychusurticae, Tetranychuscinnabarinus, Tetranychustelarius).

The composition according to the invention can be applied to any and all developmental stages of pests, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive mixtures or of compositions comprising the mixtures.

As per one embodiment the present composition can be formulated as any of the formulation mentioned above.

As per preferred embodiment, the present invention is in the form of Water Dispersible Granules (WDG), Wettable Powders (WP), and Suspension Concentrate (SC).

As per one embodiment, the pesticidal composition according to present invention is to be applied as Foliar spray with manually operated or machine operated sprayers with the spray volume of 250 ml to 5000 g or ml per hectare.
As per one embodiment, the pesticidal composition according to present invention is applied in an amount of from 100 to 4000 g or ml per hectare, preferably from 500 to 2000 g or ml per hectare, most preferably from 100 to 1000 g or ml per hectare.
The composition of present invention can be applied as preventive measure or as soon as early infestation of insects observed on crops.
The composition of the present invention in addition to Tolfenpyrad and an insecticide selected from Acephate, Chlorpyrifos, Pymetrozine, Flonicamid and Fenpyroximatefurther comprises inactive excipients including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.

A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersants are sodium lignosulphonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersants used herein include but not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.

Anti-freezing agent as used herein can be selected from the group consisting of polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol.

Water-based formulations often cause foam during mixing operations in production. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates or mixtures thereof.

Suspension aid in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof).

Biocides / Microorganisms cause spoilage of formulated products. Therefore anti-microbial agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such as sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxy benzoates or mixtures thereof.

Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, e.g. bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof. Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.

The quick coating agent can be a conventionally available sticker, for example polyesters, polyamides, poly- carbonates, polyurea and polyurethanes, acrylate polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, vinyl alcohol, vinyl acetate and vinyl pyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymers and mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), alkyd resins, and mixtures of two or more of these. Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an application environment. Examples of biodegradable polymers that are useful in the present invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch esteraliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.

Buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Potassium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.

The solvent for the formulation of the present invention may include water, water-soluble alcohols and dihydroxy alcohol ethers. The water-soluble alcohol which can be used in the present invention may be lower alcohols or water-soluble macromolecular alcohols. The term "lower alcohol", as used herein, represents an alcohol having 1-4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. Macromolecular alcohol is not limited, as long as it may be dissolved in water in a suitable amount range, e.g., polyethylene glycol, sorbitol, glucitol, etc. The examples of suitable dihydroxy alcohol ethers used in the present invention may be dihydroxy alcohol alkyl ethers or dihydroxy alcohol aryl ethers. The examples of dihydroxy alcohol alkyl ether include ethylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, dipropylene glycol ethyl ether, etc. The examples of dihydroxy alcohol aryl ethers include ethylene glycol phenyl ether, diethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, and the like. Any of the above mentioned solvent can be used either alone or in combination thereof.

The process for preparing the present novel synergistic composition can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.

EXAMPLES
Example 1: Tolfenpyrad 8%+Acephate 40% WDG (Water Dispersible Granules)
Compositions Percent (w/w)
Tolfenpyrad (97% purity) 8.76
Acephate (98% purity) 41.83
Alkylated naphtalenesulfonate, sodium salt 7.00
Sodium Polycarboxylate 3.50
Dioctylsulfosuccinate 2.50
Silicone antifoam 1.00
Precipitated silica 7.00
Polymeric carbodiimide 1.00
Starch 10.00
Hydrophobic silica 7.00
China Clay 10.41
TOTAL 100

Procedure:
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is than grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (for approx 1.5 hr)
Step 3 Homogeneous material is analysed. After getting approval from QC dept. material is unloaded into 25 kg. HDPE bag with LDPE liner inside.
Step 4 Finely grinded powder is mixer with required quantity of water to form extrudable dough.
Step 5 Dough is passed through extruder to get granules of required size.
Step 6 Wet granules are passed through Fluidised bed drier and further graded using vibrating screens.
Step 7 Final product is sent for QC approval.
Step 8 After approval material is packed in required pack sizes.

Example 2: Tolfenpyrad 20%+Pymetrozine 20% WDG (Water Dispersible Granules)
Compositions Percent (w/w)
Tolfenpyrad (97% purity) 21.13
Pymetrozine (95% purity) 21.13
Alkylated naphtalenesulfonate, sodium salt 7.00
Sodium Polycarboxylate 4.00
Sodium Lauryl Sulfate 3.00
Silicone antifoam 1.00
Lactose anhydrous 10.00
Sodium SulfateAnhydrous 3.00
Ureaformaldehyde resin powder 10.00
China Clay 19.74
TOTAL 100

Procedure: As per Example 1

Example 3: Tolfenpyrad 30%+Flonicamid 15% WDG (Water Dispersible Granules)
Compositions Percent (w/w)
Tolfenpyrad (97% purity) 32.47
Flonicamid (95% purity) 16.31
Alkylated naphtalenesulfonate, sodium salt 7.00
Sodium Polycarboxylate 5.00
Sodium Lauryl Sulfate 2.00
Silicone antifoam 1.00
Lactose anhydrous 10.00
Ureaformaldehyde resin powder 10.00
Trisiloxaneethoxylate 2.00
China Clay 14.22
TOTAL 100.00

Procedure: As per Example 1

Example 4: Tolfenpyrad 15% + Pymetrozine 15% SC (Suspension Concentrate)
Composition Percent (w/w)
Tolfenpyrad (97% purity) 15.97
Pymetrozine (95% purity) 15.97
Ethoxylated Fatty Alcohol 2.00
Nonionic polyalkylene glycol ether 1.00
Acrylic graft copolymer 3.00
Alkylated naphtalenesulfonate, sodium salt 0.50
Silicone antifoam 1.00
Benzisothiazoline 0.20
Glycol 5.00
Polysaccharides 0.20
Trisiloxaneethoxylate 3.00
Polyvinyl pyrrolidone 0.50
Water 51.66
TOTAL 100.00

Procedure:
Step 1 Gum Solution should be made 12-18 hour prior to use. Take required quantity of water, biocide, and defoamer and homogenize, then slowly add gum powder to it and stir till complete dissolution.
Step 2 Charge required quantity of DM water need to be taken in designated vessel for Flowable concentrate/ Suspension concentrate/ Flowable slurry production.
Step 3 Add required quantity of Wetting agent, dispersing agent & suspending agents, colourant/dye and homogenize the contents for 45 – 60 minutes using high shear homogenizer.
Step 4 Then add technical and other remaining adjuvants excluding ‘antifreeze & thickeners’ are added to it and homogenized to get uniform slurry ready for grinding.
Step 5 Before grinding half the quantity of antifoam was added and then material was subjected to three cycles of grinding in Dyno mill.
Step 6 Half quantity of the antifoam was added along with antifreeze after grinding process completes and before sampling for in process analysis.
Step 7 Finally add gum solution to this formulation and send to QC for quality check

Example 5: Tolfenpyrad 30% + Fenpyroximate 5% SC (Suspension Concentrate)
Composition Percent (w/w)
Tolfenpyrad (97% purity) 32.47
Fenpyroximate (96% purity) 5.72
Ethoxylated Fatty Alcohol 1.50
Nonionic polyalkylene glycol ether 2.00
Acrylic graft copolymer 3.00
Alkylated naphtalenesulfonate, sodium salt 1.00
Bentonite Clay 2.50
Silicone antifoam 1.00
Benzisothiazoline 0.20
Glycol 5.00
Polysaccharides 0.18
Polyvinyl pyrrolidone 0.50
Water 44.93
TOTAL 100.00
Procedure: As per Example 4
Example 6: Tolfenpyrad 30% + Fenpyroximate 5% EC (Emulsifiable Concentrate)
Composition Percent (w/w)
Tolfenpyrad (97% purity) 32.47
Fenpyroximate (96% purity) 5.72
Blend of calcium salt of alkyl benzene and sulfonic acid poly ethanoxy ether of benzyl phenol/ fatty alcohol 8.00
Aromatic solvent 53.81
TOTAL 100
Procedure:
Step 1 Charge the required quantity of aromatic solvent to blending vessel.
Step 2 Now charge the required quantity of technical material to the above vessel
Step 3 Send sample to QC lab for In process analysis and recommendation for emulsifier addition
Step 4 Add emulsifiers as per instruction of QC lab and homogenize for 30 minutes
Step 5 Send homogenized to QC for final testing and approval.
Step 6 Post approval unload sample in vessels/ containers of required size for storage or marketing

Example 7: Storage stability data
7.1: Storage stability Study-Tolfenpyrad 8%+Acephate 40% WDG (Water Dispersible Granules)
Parameters Specification Initial Heat stability at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Description The material shall be in the form of free flowing cylindrical extrudes devoid of any extraneous impurities Complies Complies Complies
Tolfenpyrad content 7.6 - 8.8 8.2 7.9 8.2
Acephate content 38 – 42 41.1 40.5 41.1
Tolfenpyrad suspensibility Mini 70% 97 93 97
Acephate suspensibility Mini 70% 95 95 95
pH 4 to 6 5.7 4.8 5.7
Wettability Max 30 s 10 10 10
Wet Sieve(45 micron) Mini 98.5% 99.6 99.6 99.6
Bulk Density 0.50-0.75 0.6 0.6 0.6
Moisture Content Max 2.0% 1 0.7 1

Room Temperature storage data
Parameters Specification Study Duration
1 month 6 month 12 months
Description The material shall be in the form of free flowing cylindrical extrudes devoid of any extraneous impurities Complies Complies Complies
Tolfenpyrad content 7.6 - 8.8 8.2 8.15 8
Acephate content 38 – 42 41.09 41 40.9
Tolfenpyrad suspensibility Mini 70% 97 96 93
Acephate suspensibility Mini 70% 95 95 95
pH 4 to 6 5.7 5.7 5.7
Wettability Max 30 s 10 10 10
Wet Sieve (45 micron) Mini 98.5% 99.6 99.6 99.6
Bulk Density 0.50-0.75 0.6 0.6 0.6
Moisture Content Max 2.0% 1 1 1

7.2: Storage stability Study-Tolfenpyrad 20%+Pymetrozine 20% WDG (Water Dispersible Granules)

Parameters Specification Initial Heat stability at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Description The material shall be in the form of free flowing cylindrical extrudes devoid of any extraneous impurities Complies Complies Complies
Tolfenpyrad content 19 – 21 20.2 20 20.2
Pymetrozine content 19 – 21 20.3 20 20.3
Tolfenpyrad suspensibility Mini 70% 95 93 95
Pymetrozine suspensibility Mini 70% 95 95 95
pH 7 to 9 8 7.8 8
Wettability Max 30 s 10 10 10
Wet Sieve (45 micron) Mini 98.5% 99.6 99.6 99.6
Bulk Density 0.45-0.70 0.48 0.48 0.48
Moisture Content Max 5.0% 4 1.5 4

Room Temperature Storage data
Parameters Specification Study Duration
1 month 6 month 12 months
Description The material shall be in the form of free flowing cylindrical extrudes devoid of any extraneous impurities Complies Complies Complies
Tolfenpyrad content 19 -21 20.2 20.2 20.1
Pymetrozine content 19 – 21 20.3 20.3 20.3
Tolfenpyrad suspensibility Mini 70% 95 95 95
Pymetrozine suspensibility Mini 70% 95 95 95
pH 7- 9 8 8 8
Wettability Max 30 s 10 10 10
Wet Sieve(45 micron) Mini 98.5% 99.6 99.6 99.6
Bulk Density 0.45-0.70 0.48 0.48 0.48
Moisture Content Max 5.0% 4 4 4

7.3: Storage stability Study-Tolfenpyrad 30%+Flonicamid 15% WDG (Water Dispersible Granules)
Parameters Specification Initial Heat stability at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Description The material shall be in the form of free flowing cylindrical extrudes devoid of any extraneous impurities Complies Complies Complies
Tolfenpyrad content 28.5 - 31.5 30.5 30.1 30.5
Flonicamid content 14.25 - 15.75 15.3 14.8 15.3
Tolfenpyrad suspensibility Mini 70% 95 95 95
Flonicamid suspensibility Mini 70% 95 95 95
pH 6 – 8 6.7 7 6.8
Wettability Max 30 s 12 12 12
Wet Sieve(45 micron) Mini 98.5% 99.6 99.6 99.6
Bulk Density 0.45-0.85 0.62 0.62 0.62
Moisture Content Max 2.0% 1.5 0.9 1.5

Room Temperature Storage data
Parameters Specification Study Duration
1 month 6 month 12 months
Description The material shall be in the form of free flowing cylindrical extrudes devoid of any extraneous impurities Complies Complies Complies
Tolfenpyrad content 28.5 - 31.5 30.5 30.5 30.48
Flonicamid content 14.25 - 15.75 15.3 15.3 15.21
Tolfenpyrad suspensibility Mini 70% 95 95 95
Flonicamid suspensibility Mini 70% 95 95 95
pH 6 – 8 6.7 6.7 6.8
Wettability Max 30 s 12 12 13
Wet Sieve(45 micron) Mini 98.5% 99.6 99.6 99.6
Bulk Density 0.45-0.85 0.62 0.62 0.62
Moisture Content Max 2.0% 1.5 1.5 1.5

7.4: Storage stability Study-Tolfenpyrad 15% + Pymetrozine 15% SC (Suspension Concentrate)
Specification Initial Heat stability at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description The material shall be in the form of pourable white to brown colour liquid suspension devoid of any lumps and sediment and clear liquid on top Complies Complies Complies
Tolfenpyrad content 14.25 - 15.75 15.2 14.9 15.2
Pymetrozine content 14.25 - 15.75 15.2 15.2 15.2
Tolfenpyrad suspensibility Mini 80% 96 95 96
Pymetrozine suspensibility Mini 80% 95 95 95
pH 6.0 - 7.5 6.5 6.5 6.5
Particle size D50 <3, D90 <10 2.5, 8 2.5, 8 2.9, 8
Pourability 95 % min 97 97 97
Specific gravity 1.05 – 1.15 1.1 1.1 1.1
Viscosity 350 -900 cps 600 680 600
Room Temperature Storage data
Specification Study Duration
Parameters In House 1 month 6 month 12 months
Description The material shall be in the form of pourable white to brown colour liquid suspension devoid of any lumps and sediment and clear liquid on top Complies Complies Complies
Tolfenpyrad content 14.25 - 15.75 15.2 15.2 15.18
Pymetrozine content 14.25 - 15.75 15.2 15.23 15.2
Tolfenpyrad suspensibility Mini 80% 96 96 95
Pymetrozine suspensibility Mini 80% 95 95 95
pH 6.0 - 7.5 6.5 6.5 6.5
Particle size D50 <3, D90 <10 2.5, 8 2.5, 8 2.5, 8
Pourability 95 % min 97 97 97
Specific gravity 1.05 – 1.15 1.1 1.1 1.1
Viscosity 350 -900 cps 600 610 610
7.5: Storage stability Study-Tolfenpyrad 30% + Fenpyroximate 5% EC (Emulsifiable Concentrate)
Specification Initial Heat stability at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 7 days
Parameters In House
Description The material shall be in form of clear transparent liquid of brown to amber colour, devoid of any suspended particles and sediments. It shall readly form emulsion upon dilution with water Complies Complies Complies
Tolfenpyrad content 28.5 - 31.5 30.33 30 30.21
Fenpyroximate content 4.75 - 5.50 5.2 5 5.2
Acidity/ Alkalinity 0.50% w/w Max 0.25 0.48 0.25
Specific gravity 1.05 – 1.15 1.1 1.1 1.1
Cold Test No crystal formation Complies Complies Complies
Flash point (Abel) Shall be more than 24.50C Complies Complies Complies
Emulsion stability (after 2 hour in 342 ppm & 700ppm standard hard water Emulsion shall be milky white, with blue shade and blooming.- Neither separation of cream on top or sedimentation at bottom Complies Complies Complies

Room Temperature Storage data
Specification Study Duration
Parameters In House 1 month 6 month 12 months
Description The material shall be in form of clear transparent liquid of brown to amber colour, devoid of any suspended particles and sediments. It shall readly form emulsion upon dilution with water Complies Complies Complies
Tolfenpyrad content 28.5 - 31.5 30.33 30.3 30.21
Fenpyroximate content 4.75 - 5.50 5.2 5.2 5.18
Acidity/ Alkalinity 0.50% w/w Max 0.25 0.27 0.27
Specific gravity 1.05 – 1.15 1.1 1.1 1.1
Cold Test No crystal formation Complies Complies Complies
Flash point (Abel) Shall be more than 24.50C Complies Complies Complies
Emulsion stability (after 2 hour in 342 ppm & 700ppm standard hard water Emulsion shall be milky white, with blue shade and blooming.- Neither separation of cream on top or sedimentation at bottom Complies Complies Complies

Example 8: Field efficacy trials
Bioefficacy :-
Rice (Oryza sativa L.) is the primary source of food for more than half of the world’s population. Insect pests and diseases are causing severe losses in rice production. Among the various insect pests, Hoppers are among the most important pests of rice. Up to 60% yield loss is common in many Asian countries. Farmers in coastal belt of south and East Indian state are regularly going for 3 to 4 sprays for control of hoppers. Due to its typical life cycle and multiple exposures to different group of insecticides in short span, it develops resistance very fast.
Considering the above objective, Tolfenpyrad with various insecticides has been tested against Rice hoppers to evaluate its efficacy.

Trial 1
To determine the level of synergism between Tolfenpyrad and various insecticides, a pot experiment was carried out with four replications and ten treatments. Four to five rice seedlings of 30 days old were planted in plastic pot. These pots were put into plastic trays full of water to maintain standing water condition. Plants were sprayed by hand atomizer with required concentration of insecticides and one untreated check was maintained that was sprayed with water only. Plants in the pots were covered with cylindrical cages. Average 20 adults of BPH (Brown Planthopper, Nilaparvatalugens) released per cage and the open end was covered with cloth. After exposure to the treated plants, insects were observed for mortality at different time intervals. Generally moribund insects were considered as dead. Number of dead insects was recorded at 24, 48, 72 and 96 h after exposure. The relative toxicity was worked out.

% Mortality = 100 x No. of dead insects / No. of treated insects.

If any insect mortality observed in untreated, than % corrected mortality was calculated as below:

% Corrected Mortality = 100 x ( T- C) / (100 – C)
Where T = Percent mortality in treatment, C= Percent mortality in Control or Untreated

The % mortality data were used to calculate the synergism between two insecticides given by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two active components can be calculated as follows:

E = X + Y - __ XY ___
100

in which E represents the expected percentage of Insecticidal control for the combination of the two insecticide at defined dose (for example equal to x and y respectively), X is the percentage of insecticidal control observed by active ingredient I at defined dose (equal to x) and Y is the percentage of insecticidal control observed by Active Ingredient II (equal to Y). When the percentage of insecticidal control observed for the combination is greater than the expected percentage, there is a synergistic effect. (Ratio of O/E > 1, means synergism observed.)

Table 1: Synergistic activity of Tolfenpyrad and other insecticides against Rice Brown Plant Hopper (Nilaparvatalugens)
Treatment Details % BPH Mortality
Obs.Value
(O) Cal.Value
(E) Ratio (O/E)
Tolfenpyrad 150 + Pymetrozine 150 ppm 99.64 82.33 1.21
Tolfenpyrad 150 + Flonicamid 75 ppm 93.12 76.57 1.22
Tolfenpyrad 150 + Acephate 1000 ppm 90.16 62.29 1.45
Tolfenpyrad 150 + Chlorpyrifos 1000 ppm 91.26 65.05 1.40
Tolfenpyrad 150 ppm 52.48
Pymetrozine 150 ppm 62.82
Flonicamid 75 ppm 50.7
Acephate 1000 ppm 20.64
Chlorpyrifos 1000 ppm 26.46

The results of pot experiment on rice BPH indicate high synergistic activity between Tolfenpyrad and one more insecticides from Pymetrozine, Flonicamid, Acephate or Chlorpyrifos.

Trial 2
Another field experiment was conducted in coastal area of southern state of Andhra Pradesh state. The experiment was conducted in Randomized Block used with 7 m X 7 m net plot size and 30 sets of treatments including one Untreated check and seven sets of prior art samples. The Rice crop was raised with all standard agronomic practices. Spraying was done with back pack sprayer with 500 liter of water spray volume. The experiment initiated when moderate incidence of BPH was observed. The observations were recorded by counting the no. of hoppers per hill (20 hills per plot). The observations were recorded at before spraying and 5, 10 and 15 days after spraying. The field observations were presented in below table. The observations on beneficial insects i.e. Spider and Predatory insects were also recorded along with hopper count. The efficacies of various treatments were also judged at the time of harvest by considering grain yield.

Table 2: Field efficacy of Tolfenpyrad and its combinations against Rice BPH (Nilaparvatalugens)
Treatments details Dose (gai/h) No. of Hoppers per hill
BS 5 DAA 10 DAA 15 DAA
Tolfenpyrad 8%+Acephate 40% WDG 90+450 43.28 10.82 4.66 14.48
Tolfenpyrad 8%+Chlorpyrifos 40% WDG 90+450 45.62 11.94 6.80 17.26
Tolfenpyrad 20%+Pymetrozine 20% WDG 90+90 39.76 2.36 0.26 0.12
Tolfenpyrad 30%+Flonicamid 15% WDG 90+45 42.58 4.82 2.64 1.26
Tolfenpyrad 20% WDG 90 38.92 10.26 16.92 24.74
Acephate 40% WDG 450 44.20 26.92 48.60 82.72
Pymetrozine 20% WDG 90 40.64 12.64 18.62 26.82
Flonicamid 15% WDG 45 36.88 16.82 24.64 34.16
Untreated Check - 37.62 52.28 79.40 98.82
WDG – Water Dispersible Granules, BS Before Spray, DAA Days After Application or Spray

The field efficacy observations were also found in line of pot experiments. The ready mix formulation of Tolfenpyrad with more insecticide from Acephate, Chlorpyrifos, Pymetrozine or Flonicamid were highly efficacious against rice BPH and also provides longer residual control as compared to their individual application.

Table 3: Safety of Tolfenpyrad and its combinations to the beneficial insects of Rice crop eco-System
Treatments details Dose (gai/h) No. of beneficial insects per hill
Spider Chysopa
BS 15 DAA BS 15 DAA
Tolfenpyrad 8%+Acephate 40% WDG 90+450 1.60 5.60 3.20 8.40
Tolfenpyrad 8%+Chlorpyrifos 40% WDG 90+450 2.20 6.20 2.60 7.60
Tolfenpyrad 20%+Pymetrozine 20% WDG 90+90 1.60 5.20 2.80 8.20
Tolfenpyrad 30%+Flonicamid 15% WDG 90+45 2.40 5.80 3.20 7.80
Tolfenpyrad 20% WDG 90 1.80 5.40 2.80 8.00
Acephate 40% WDG 450 2.00 4.20 3.40 7.40
Pymetrozine 20% WDG 90 2.20 5.00 3.20 7.80
Flonicamid 15% WDG 45 2.40 4.60 2.60 8.00
Untreated Check - 1.80 5.60 3.00 8.20

All the synergistic ready mix formulation of Tolfenpyrad and one more insecticides are found to be safe for beneficials like Spider and Chyrsopa found in rice crop ecosystem.

Trial 3
A pot experiments was carried out on Cotton (Gossypium hirsutum) to find the synergism between Tolfenpyrad and Flonicamid. The required concentration of Tolfenpyrad and Flonicamid were prepared and sprayed on Cotton plant raised in plastic pot. The cotton plants were allowed to natural infestation of leaf hopper Amrascabiguttulabiguttula. The number of insects were counted before spray and 72 hrs after spray and % corrected mortality was calculated as per the formula given in Trial 1. The synergistic ratio was calculated by Colby’s formula (As per Trial 1).

Table 4: Synergistic activity of Tolfenpyrad and Flonicamid against Cotton Leaf hopper, Amrascabiguttulabiguttula
Compositions % Leaf Hopper control
Obs.Value Cal.Value Ratio
Tolfenpyrad 150 + Flonicamid 75 ppm 98.8 76.01 1.30
Tolfenpyrad 150 ppm 42.6
Flonicamid 75 ppm 58.2

Tolfenpyrad and Flonicamid show synergistic activity against cotton leaf hopper.

Trial 4
A pot experiments was carried out on Brinjal (Solanum melongena)to find the synergism between Tolfenpyrad and Fenpyroximate. The required concentration of Tolfenpyrad and Flonicamid were prepared and sprayed on Brinjal raised in plastic pot. The Brinjalplants were allowed to natural infestation of red spider mite Tetranychus urticae. The number of motile stages of mite were counted before spray and 72 hrs after spray and % corrected mortality was calculated as per the formula given in Trial 1. The synergistic ratio was calculated by Colby’s formula (As per Trial 1).

Table 5: Synergistic activity of Tolfenpyrad and Fenpyroximate against Brinjal red spider mite, Tetranychus urticae
Compositions % Red Spider Mite control
Obs.Value Cal.Value Ratio
Tolfenpyrad 150 + Fenpyroximate 30 ppm 92.4 79.02 1.17
Tolfenpyrad 150 ppm 43.6
Fenpyroximate 30 ppm 62.8

The pot experiments data shows synergism between Tolfenpyrad and Fenpyroximate against red spider mite efficacy.
,CLAIMS:We claim;
1. A synergistic insecticidal composition comprising bioactive amounts of Tolfenpyrad and an insecticide selected from Acephate, Chlorpyrifos, Pymetrozine, Flonicamid and Fenpyroximate with one or more inactive excipients.
2. The synergistic insecticidal composition as claimed in claim 1, wherein the ratio of Tolfenpyrad and an insecticide selected from Acephate, Chlorpyrifos, Pymetrozine, Flonicamid and Fenpyroximate is 1:10 to 10:1.
3. The synergistic insecticidal composition as claimed in claim 1, wherein inactive excipients can be selected from the group consisting of dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents and buffering agent.
4. The synergistic insecticidal composition as claimed in claim 1, wherein the composition are selected from and Water Dispersible Granules (WDG), Wettable powder (WP) and Suspension Concentrate (SC).
5. The synergistic insecticidal composition as claimed in claim 1, wherein the said composition is to be used in management of insect or pastes in GMO and Non GMO of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticumaestavum), Barley (Hordeumvulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Sugarcane (Saccharumofficinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachishypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linumusitatissimum), Sesame (Sesamumindicum), Castor (Ricinuscommunis), Green gram (Vigna radiate), Black gram (Vignamungo), Chickpea (Ciceraritinum), Cowpea (Vignaunguiculata), Redgram (Cajanuscajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotylomauniflorum), Field pea (Pisumsativum), Cluster bean (Cyamopsistetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanumlycopersicun) , Potato (Solanumtuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumissativus), Muskmelons (Cucumismelo), Watermelon (Citrulluslanatus), Bottle gourd (Lagenariasiceraria), Bitter gourd (Momordicacharantia), Radish (Raphanussativus), Carrot (Dacuscarota subsp. sativus), Turnip (Brassica rapasubsprapa), Apple (Melusdomestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitisvinifera), Guava (Psidiumguajava), Litchi (Litchi chinensis), Mango (Mangiferaindica), Papaya (Carica papaya), Pineapple (Ananascomosus), Pomegranate (Punicagranatum) , Sapota (Manilkarazapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiberofficinale), Cumin (Cuminumcyminum), Fenugreek (Trigonellafoenum-graecum), Fennel (Foeniculumvulgare), Coriander (Coriandrumsativum), Ajwain (Trachyspermumammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safedmusli (Chlorophytumtuberosum), Drum stick (Moringaoleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellisperennis), Dahlia (Dahlia hortnesis), Gerbera ( Gerbera jamesonii), Carnation (Dianthus caryophyllus).

6. The synergistic insecticidal composition as claimed in claim 5, wherein the composition is used to control insects-pets belongs to Lepidopteran insects, Chilopartellus, Chilosuppressalis, Cydiapomonella, Plutellaxylostella, Peirisrapae, beetles (coleopteran), e.g. Dicladispaarmigera, Phyllotretanemorum, Phyllotretastriolata, flies (Diptera), e.g. Atherigonaorientalis, Dacuscucurbi-tae, Dacusoleae, Liriomyzasativae, Liriomyzatrifolii, Melanagromyza obtuse, Ophiomyiaphaseli, thrips (Thysanoptera), e.g. Frankliniellaoccidentalis, Scirtothripscitri, Scirtothrips dorsalis, Thrips oryzae, Thrips palmi and Thrips tabaci, true bugs (Hemiptera), e.g. Amrascabiguttulabiguttula, Amrascadevastans, Amritodusatkinsoni, Aphis fabae, Aphis pomi, Aphis gossypii, Aphis crassivora, Bemisiaargentifolii, Bemisiatabaci, Brevicorynebrassicae, Clavigrallagibbosa, Dysdercuscingulatus, Idioscopus spp., Leptocorisaacuta, Lyguslineolaris, Myzuspersicae, Nilaparvatalugens, Nephotettixvirescens, Nephotettixnigropictus, Planococcus spp., Pseudococcus spp., Pyrillaperpusilla, Psylla mail, Psyllapiri, Rhopalomyzusascalonicus, Rhopalosiphummaidis, Rhopalosi-phumpadi, Rhopalosiphuminsertum, Sappaphis mala, Sappaphis mail, Schizaphisgraminum, Schizoneuralanuginosa, Sitobionavenae, Sogatellafurcifera, Trialeurodesvaporariorum, Toxopteraaurantiia, Psylla spp., Rhopalosiphum spp., Sitobion spp., crickets, grasshoppers, locusts (Orthoptera), e.g. Gryllotalpagryllo-talpa, Locustamigratoria, Melanoplusbivittatus, Locustanapardalina., from the order Acarina, for example, Brevipalpus spp., Eriophyes spp., Olygonychuscoffeae, Panonychus spp., Polyphagotarsonemuslatus, Tarsonemus spp. and Tetranychus spp. (Tetranychusurticae, Tetranychuscinnabarinus, Tetranychustelarius).

7. The synergistic insecticidal composition of Tolfenpyrad and an insecticide selected from Acephate, Chlorpyrifos, Pymetrozine, Flonicamid and Fenpyroximateclaimed in any of the preceding claims and exemplified with working examples as disclosed.