Description:FIELD OF THE INVENTION:

The present invention relates to synergistic ternary agrochemical composition comprising Compound (A) N1 -[1,1-dimethyl-2(methyl sulfonyl) ethyl]-3-iodo-N-{4- [1,2,2,2-tetrafluoro-l-trifluoromethyl)ethyl}-0- tolyl}phthalimide, known as Formula I; Compound (B), (E)-1(2-chloro-1, 3-thiazol-5-ylmethyl)-3-methyl-2- nitroguanidine, known as Formula II; Compound (C) selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride; and d) one or more inactive excipients. The present invention further relates to process of preparing said composition and its use as insecticide.

BACKGROUND OF THE INVENTION:

Indian Patent Number: 350127 (Patent Application Number: 201621008707): It teaches about synergistic composition of thiocyclam hydrogen oxalate and Clothianidin, and thiocyclam hydrogen oxalate and cartap hydrochloride.

Indian Patent Number: 531002 (Patent Application Number: 201821014060): It discloses ternary granular insecticidal composition of chlorantraniliprole+clothianidin+cartap hydrochloride and chlorantraniliprole+clothianidin+thiocyclam hydrogen oxalate.

Indian Patent Application Number: 202021051797: It discloses quick release insecticidal composition comprising of chlorantraniliprole and cartap hydrochloride.

Indian Patent Application Number: 202311025504: It discloses synergistic granular insecticidal composition comprising of chlorantraniliprole, fipronil and emamectin benzoate.

Flubendiamide is a new insecticide which specifically targets immature lepidoptera pests. It represents a new class of insecticide, pthalmic acid diamides. Flubendiamide works by activating the ryanodine receptor which regulates muscle and nerve activities by modifying levels of calcium in these cells. Ryanodine receptor activation results in rapid cessation of feeding followed by death and also exhibits residual larvicidal activity. Flubendiamide exhibits no cross-resistance with conventional insecticides and should therefore provide a new tool for management of lepidopteran insecticide resistance.
Clothianidin is an insecticide developed by Takeda Chemical Industries and Bayer AG. Similar to thiamethoxam and imidacloprid, it is a neonicotinoid. Neonicotinoids are a class of insecticides that are chemically similar to nicotine, which has been used as a pesticide since the late 1700s. Clothianidin and other neonicotinoids act on the central nervous system of insects as an agonist of nAChR, the same receptor as acetylcholine, the neurotransmitter that stimulates and activating post-synaptic acetylcholine receptors but not inhibiting AChE. Formula II and other neonicotinoids were developed to last longer than nicotine, which is more toxic and which breaks down too quickly in the environment.

Thiocyclam hydrogen oxalate is an organosulfur heterocyclic compound that is 1,2,3-trithiane in which one of the hydrogens at position 5 has been replaced by a dimethylamino group. A nicotinic acetylcholine receptor agonist, it was used (particularly as its hydrogen oxalate salt, known as thiocyclam oxalate) as a broad-spectrum insecticide, but it is also toxic to bees, fish and other aquatic organisms. It is not approved for use within the European Union. It has a role as an herbicidal and a nicotinic acetylcholine receptor agonist. It is a nereistoxin analogue insecticide and an organosulfur heterocyclic compound. It is a conjugate base of a thiocyclam (1+). It derives from a hydride of a 1,2,3-trithiane.

Cartap hydrochloride is an insecticide of Nereistoxin analogue group, which gives effective control on insect’s pests and considered as best stem borer insecticide. Cartap SP controls all stages of insects (egg, larva, adult). It is compatible with commonly used insecticide and fungicide.
Cartap hydrochloride is an insecticide of Nereistoxin analogue group, functioning as a potent insecticide that effectively manages insect pests, particularly excelling in controlling stem borers. Cartap exhibits control over all stages of insects, including eggs, larvae, and adults. Additionally, it demonstrates compatibility with commonly utilized insecticides and fungicides.

Insecticide compositions typically consist of an active ingredient that targets specific pests, along with several inert ingredients that aid in the formulation's effectiveness, stability, and ease of application. The active ingredient is often a chemical compound such that disrupts the biological processes of insects, either by affecting their nervous system or interfering with their metabolic functions. Inert ingredients, which can include solvents, emulsifiers, stabilizers, and carriers, help to dissolve, dilute, or spread the active ingredient more efficiently, ensuring uniform coverage and enhancing its persistence on surfaces. Some formulations may also contain surfactants to improve the spread ability of the insecticide, or fragrances to mask odours. The precise combination of these components is designed to optimize both the potency and safety of the insecticide, ensuring effective pest control while minimizing risks to humans, animals, and the environment.

In general use, the insecticides actives are used in the form of a dilute aqueous composition because it can attain a good interaction with the target organism. However, most active insecticide compounds that are used as insecticides are only sparingly or even insoluble in water. The low solubility of such compounds presents the challenges and difficulties to formulator in formulating pesticide compounds in stable formulations that can be easily stored for a long time and which still have a high stability and effective activity until end use. This problem especially occurs and may get worsen if more than one active compound is present in the composition.

However, there remains a need for a synergistic ternary composition that addresses the limitations of current formulations. Such a composition should effectively overcome existing issues while being amenable to straightforward and cost-effective manufacturing processes. This formulation should provide enhanced insecticidal activity through synergistic interactions among its components yet be simple to produce without requiring complex or resource-intensive production methods.

Therefore, there still exists a need to develop ternary composition, which is stable, synergistic, more effective in control of wide spectrum of insect-pests in crop and environmentally safe.

Another objective of the present invention is to provide a synergistic ternary one-shot composition effective for controlling undesired insect-pests on crop for long duration.

Yet another objective of the present invention is to provide a synergistic ternary composition which is safe to the crops.

Yet another objective of the present invention is to provide a process for the preparation of a synergistic ternary composition comprising the active ingredients of the present invention and excipients suitable for such an insecticidal composition.

Therefore, an aspect of the present invention is to provide novel synergistic agrochemical composition comprising compound (a) Formula I; compound (b) Formula II; compound (c) selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride; and d) one or more inactive excipients can provide solution to the above-mentioned problems.
Further Inventors of the present invention have surprisingly found that the novel synergistic agrochemical composition comprising compound (a) Formula I; compound (b) Formula II; compound (c) selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride; and d) one or more inactive excipients provides synergistic effect.

The present invention further relates to process of preparing said composition along with at least one inactive formulation excipients and formulation thereof which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.

SUMMARY OF THE INVENTION
The main aspect of the present invention provides a synergistic ternary agrochemical composition comprising:
a. Compound (A) Formula I N1 -[1,1-dimethyl-2(methyl sulfonyl) ethyl]-3-iodo-N-{4- [1,2,2,2-tetrafluoro-l-trifluoromethyl)ethyl}-0- tolyl}phthalimide;
b. Compound (B) Formula II (E)-1(2-chloro-1, 3-thiazol-5-ylmethyl)-3-methyl-2- nitroguanidine;
c. Compound (C) selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride; and
d. One or more inactive excipients.

Another aspect of the present invention to provide synergistic ternary agrochemical composition comprises: Compound (A) Formula I is in amount of 0.1% to 10% w/w; compound (B) Formula II is in amount of 0.1% to 10% w/w; and compound (C) is selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride is in amount of 1% to 75% w/w.
Another aspect of the present invention to provide one or more inactive excipients is selected from wetting agent, dispersing agent, disintegrating agent, emulsifier, defoamer, filler, pH stabilizer, anticaking agent, filler, solvent or a combination thereof and other additives, if required in a formulation.

The synergistic ternary agrochemical composition of the present invention formulated as dry formulations, such Water dispersible granules/Wettable Granule (WDG/WG), Water soluble granules (SG), Emulsifiable granule (EG), Wettable powder (WP), Water Dispersible Powder (WDP), Soluble powder (SP), Emulsifiable powder (EP), Oil dispersible powder (OP), Soluble Tablet (ST), Granules (GR) for soil application, Controlled (Slow or Fast release) Release Granule (CR-GR).

Further aspect of the present invention is to provide synergistic, broad-spectrum control of harmful insect-pests infesting crop.

DETAILED DESCRIPTION OF THE INVENTION:

In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar compounds, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here. The present technology is also illustrated by the examples herein, which should not be construed as limiting in any way.

As used herein, the terms below have the meanings indicated.

The singular forms "a," "an," and "the" may refer to plural articles unless specifically stated otherwise.

The term "about," as used herein, is intended to qualify the numerical values which it modifies, denoting such a value as variable within a margin of error. When no particular margin of error, such as a standard deviation to a mean value given in a chart or table of data, is recited, the term "about" should be understood to mean that range which would encompass the recited value and the range which would be included by rounding up or down to that figure as well, taking into account significant figures.

The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of” will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not specified.

As used herein, the term “excipient” refers to inert substances which are commonly used as diluent, to provide stability or to increase the activity profile of the composition or formulation without having any insecticidal activity or direct effect on the insect pests.

The present invention relates a synergistic ternary agrochemical composition comprising:
a. Compound (A) Formula I;
b. Compound (B) Formula II;
c. Compound (C) is selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride; and
d. One or more inactive excipients.

Another aspect of the present invention to provide a synergistic ternary agrochemical composition comprises: Compound (A) Formula I is in amount of 0.1% to 10% w/w; compound (B) Formula II is in amount of 0.1% to 10% w/w; and compound (C) is selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride is in amount of 1% to 75% w/w.

The composition of the present invention comprises excipients selected from solvent, emulsifier, wetting agent, dispersing agent, antifoaming agent/defoamer, thickener/suspending agent, anti-freezing agent, biocide/preservative, disintegrating agent, wall forming materials, anti-caking agent, filler and/or a combination thereof. The composition may also contain if desired, one or more auxiliary customary for crop protection compositions.

The synergistic ternary agrochemical composition of the present invention formulated as dry formulations, such Water dispersible granules/Wettable Granule (WDG/WG), Water soluble granules (SG), Emulsifiable granule (EG), Wettable powder (WP), Water Dispersible Powder (WDP), Soluble powder (SP), Emulsifiable powder (EP), Oil dispersible powder (OP), Soluble Tablet (ST), Granules (GR) for soil application, Controlled (Slow or Fast release) Release Granule (CR-GR).

The composition of the present invention is effective to control various insects-pests belongs to the order Hemiptera, for example, aphid, jassid, leaf hopper, mango hopper, whitefly, mealybug, scale, rice brown plant hopper (BPH), leaf hopper; order Lepidoptera, fall army worm, rice stem borer, rice leaf folder, sugarcane early shoot borer, top borer, wheat pink stem borer, fruit borer, pod borer, plume moth, maruca, cut worm, diamond back moth (DBM), looper, semi looper, pink bollworm, brinjal fruit and shoot borer, spodoptera spp. (litura, exigua, frugiperda), heliothis/helicoverpa; from the order Coleoptera, white grub, wire worm, epilachna beetle, blue beetle, girdle beetle, flea beetle, rice water weevil; from the order Orthoptera, for example, locust; from the order Thysanoptera, for example, cotton thrips, chilli thrips, black thrips; from the order Isoptera, example-termite; from the order Diptera, for example, shoot fly, stem fly, fruit fly, leaf miner; from the order Acarina, for example, red mite, red spider mite, pink mite, broad mite, purple mite.

The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidal effective amount of inventive compositions.

The crops and plants treated by present compositions are comprises of genetically modified varieties or hybrid varieties or conventional varieties of paddy/rice, wheat, maize, sugarcane, cotton, okra, brinjal, chilly, tomato, cabbage, cauliflower, tomato, potato, garlic, onion, groundnut, soybean, green gram, black gram, red gram, chickpea, cucumber, melons, apple, mango, papaya, pomegranate, banana, grapes, tea, coffee, cumin, fennel, black pepper, flower crops like rose, marigold etc.

The synergistic ternary agrochemical compositions are applied as a spraying (by diluting into water), broadcasting or fertigation. The spraying can be done by manually or battery-operated backpack sprayer, spray machines, tractor operated sprayer, UAV arial application (example drone). Broadcasting of granules can be done manually or by machine.

Compound A Compound B Compound C
Formula I

Formula II

Thiocyclam hydrogen oxalate or Cartap hydrochloride
Broad range, w/w 0.1 to 10 0.1 to 10 1 to 75
Narrow range, w/w 0.2 to 7 0.4 to 6 2 to 65

Further, synergistic ternary agrochemical compositions comprising compound (a) Formula I; compound (b) Formula II; compound (c) selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride; and d) one or more inactive excipients.

In further aspect the present invention relates to synergistic ternary agrochemical composition comprising compound (A) Formula I is in amount of 0.1% to 10% w/w, preferably 0.2% to 7% w/w; compound (B) Formula II is in amount of 0.1% to 10% w/w, preferably 0.4% to 6% w/w; and compound (C) selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride is in amount of 1% to 75% w/w, preferably 2% to 65% w/w.

The composition of the present invention comprises agriculturally acceptable excipients selected from wetting agent, dispersing agent, disintegrating agent, emulsifier, defoamer, anti-freezing agent, biocide, filler, thickener/suspending agent, pH stabilizer, anticaking agent, filler, solvent or a combination thereof and other additives, if required in a formulation.

Wetting agent:
Wetting is the first stage of dispersion, in which air surrounding the granular composition is substituted with water. Wetting of the composition with water cannot occur if the surface tension of the liquid is very high. Hence, it is recommended to add a wetting agent to the composition to facilitate the process of dispersion of the granules in the liquid. Non-limiting examples of wetting agents that can be used in the present invention include, but not limited to, tristyryl phenol ethoxylate non-ionic polymer, sodium iso propyl naphthalene sulphonate, alkyl phenyl ethoxylate, aryl phenyl ethoxylate, aryl phenyl ether phosphate, alkoxylated alcohol, ethoxylated fatty alcohol, ethylene oxide-propylene oxide (EO-PO) block copolymer, alkyl aryl sulphonate, alkyl olefin sulfonate, dioctyl succinate, sodium lauryl sulfate, alkyl polyglucoside, sodium alkyl aryl taurate, sorbitol esters, sorbitol oleate, poly aryl phenyl ether phosphate, polyalkoxylated butyl ether, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, alkyl naphthalene sulfonate. Ethoxylated alcohol includes natural fatty alcohol (lauryl alcohol ethoxylate, lauryl alcohol alkoxylate), synthetic alcohol ethoxylate (tridecyl alcohol ethoxylate, 2-ethyl hexanol, 2-propylheptanol, isodecyl alcohol, trisiloxane ethoxylate, heptamethyl trisiloxane, modified form includes polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, polyalkyleneoxide modified Tri siloxane, polyalkyleneoxide modified polydimethylsiloxane, may be liquid or powder form.
One or more wetting agents may be used in the present composition.
The wetting agent is present in an amount in the range from 1 to 10% w/w.

Dispersing agent:
Dispersing agents /surfactants are added to prevent agglomeration of solid particles in a liquid and keep them suspended in fluid. Accordingly, the composition of the present invention contains the dispersing agent selected from the group comprising polyacrylate compound selected from a homopolymer, a block-copolymer or a random copolymer and the mixtures thereof. Polyacrylate compound selected from a group comprises poly(methyl acrylate), poly(ethyl acrylate), poly(propyl acrylate), poly(n-butyl acrylate), poly(isobutyl acrylate), poly(2-ethyl acrylate), poly(t-butyl acrylate), poly(ethylhexyl acrylate), poly(benzyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate), poly((ethylene glycol) methyl ether methacrylate), poly(methacrylate-coethylacrylate), poly(methacrylate-co-styrene), poly(methacrylate-co-butylmethacrylate), poly(n-butylmethacrylcate-co-methacrylate), poly((ethylene oxide)-co-poly(methyl acrylate)), polymethyl methacrylate-polyethylene glycol graft copolymer (Atlox 4913), nonionic comb-shaped polyacrylate (Dispersogen PSL 100), 2-Acrylamido-2-Methylpropane Sulfonic Acid, Sodium methallyl sulfonate, 3-sulfopropyl acrylate potassium salt, 3-sulfopropyl methacrylate potassium salt, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxymethyl methacrylate, Polyethylene-g-poly(n-butyl acrylate), and the mixtures thereof. Polyarylphenyl ether phosphate, Tri styryl phenol ethoxylate, ethoxylated tristryl phenol sulphate, acrylic polymer amine salt, naphthalene sulfonic acid-sodium salt condensate with formaldehyde, alkylated naphthalene sulfonate-sodium salt, ethoxylated oleylcetyl alcohol, poly alkelene glycol ether, ethoxylated fatty alcohol, alkyl sulfonate, styrene acrylic copolymer, alkyl phenol polyglycol ether, sodium lignosulfonate, calcium lignosulfonate, sodium polycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propylene oxide- polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycol ether-phosphate, tristyrylphenole with 16 moles EO, oleyl-polyglycol ether with ethylene oxide, tallow fatty amine polyethylene oxide, nonylphenol polyglycol ether with 9-10 moles ethylene oxide.
One or more dispersing agents is used in the present composition in an amount in the range from 1 to 25% w/w.

Emulsifier
An emulsifier helps to prevent the droplets of the dispersed phase of an emulsion from flocculating or coalescing in the emulsion. Suitable emulsifier is used herein, but not limited to castor oil ethoxylate 40 mole, Polyoxyethylenealkylphenyl ether alkyl aryl sulfonate, 3-methoxy N, N-dimethyl propionamide, Polyglyceryl-3 caprylate, Polysorbate 60 (polyoxyethylene sorbitan monostearate-Tween 60), solvents alkyl phenol, aryl phenol, alkyl phenol ethoxylate, fatty acid esters, fatty acid alkanol amides, alkoxylated fatty acid ester or a combination thereof.
The emulsifier is present in an amount in the range from 1 to 50% w/w.

Solvent:
The solvent and cosolvent used in the present invention is selected from the group comprising of demineralized (DM) water, alcohols such as ethanol, propanol, n-octanol, isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, acetophenone, glycerin, polyol ethers such as ethylene glycol monopropyl ether, diethylene glycol, monomethyl ether, Di propylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, isoparaffin, kerosene, mineral oil; heavy aromatic hydrocarbons such as mixture of heavy aromatic naphtha hydrocarbon C-9 to C-16, xylene, toluene, naphthalene, solvent naphtha, solvent C9, solvent C10, solvent C12, solvesso 100, solvesso 150, solvesso 200; carboxamide; aliphatic or aromatic hydrocarbons such as chlorobenzene, chloroethylene, methylene chloride; esters such as ethyl acetate, Di isopropyl phthalate, dimethyl adipate, methyl oleate, methyl tallowate; lactones such as gamma-butyrolactone; alkyl amide, amides such as dimethylformamide, alkyl pyrrolidone, N-methyl-2-pyrrolidone, N-octyl pyrrolidone, N,N-dimethyldecanamide, N, N-dimethyloctanamide, N, N-dimethylamine, N,N-dimethylmethanamide; nitriles such as acetonitrile; organosulfur compound such as alkyl sulfoxide, dimethyl sulfoxide, propylene carbonate, mineral oil, methylated seed oil-methyl ester of palm oil/soybean oil/castor oil/cotton seed oil/blend of two or more seed oil.
The solvent may be used alone or in combination and is present in an amount quantity sufficient (QS) required to make 100% w/w formulation.
Castor oil ethoxylate 40 moles is non-ionic surfactant that is derived from castor oil. It has variety of uses such as emulsifier, wetting agent, dispersing agent, additive, antistatic agent and as a solvent.

Disintegrating agent:
Inert material such as clays, bentonite, diatomaceous, colloidal silica, kaolin which swell by water absorption improve in dispersibility. Water soluble salts such as potassium phosphate, ammonium sulphate, sodium sulphate, sodium citrate or urea can be also used as disintegrating agent in an amount in the range from 1% to 25% w/w.

pH Stabilizer
pH stabilizers may include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, potassium hydrogen phosphate salt solution, acetic acid & sodium acetate, ammonia & ammonium chlorides, citric acid, benzoic acid, salicylic acids, hydrochloric acid, phosphoric acid, sodium citrate, soda ash, carboxylic acids, 2,6-di-tert-butyl-p-cresol, butylhydroxyanisole (BHT), epoxidized soybean oil (ESBO), methyl oleate, potassium carbonate, potassium hydroxide, sodium hydroxide and sodium dihydrogen phosphate dihydrate or combination thereof. Optionally stabilizer present in an amount in the range from 0.05 to 2% w/w.

Anticaking agent
Anti-caking agents are used to prevent caking, which is the formation of lumps. They also make packaging, transport, flowability, and consumption easier. The anticaking agent may be selected from silica/silicone dioxide, calcium silicate, and sodium ferrocyanide. Calcium stearate. Optionally anti-caking agents are present in an amount in the range from 0.1 to 10% w/w.

Humectant
Humectant selected from urea, glycerol or lactose and optionally present in an amount in the range from 0.1 to 2% w/w.

Binder
The binder is water soluble, water swellable or combinations of both. The binder is a water-
soluble binder selected from a group consisting of poly ethylene wax, poly vinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene oxide, polyethoxylated fatty acids, polyesters, polyamides, poly carbonates, poly urea, poly urethanes, styrene copolymer, butadiene copolymers, polyethoxylated alcohols, acrylate polymer such as polymethacrylate, poly ethyl methacrylate, poly methyl methacrylate, acrylate copolymers and styrene-acrylic copolymers or mixtures of thereof, a natural gum, lignosulphonate, and a combination thereof. The binder is a water swellable binder selected from a group consisting of China clay, bentonite, fuller’s earth, zeolite, quartz, precipitated silica, palygorskite, sepiolite, halloysite, and a combination thereof. Binder is present in an amount in the range from 0.1 to 10% w/w.

Precipitated silica acts as carrier material, absorbing and holding the active ingredient while maintaining a free flowing, easily dispersible powder form, enhancing wettability by improving water contact, and often providing anti-caking properties to prevent clumping, making it crucial for consistent application of the pesticide when mixed with water for spraying on crops.

Filler/Carrier
A filler/carrier selected from the group comprising sand, silica, precipitated silica, bentonite, attapulgite, ceramic, montmorillonite, pumice, sepiolite, diatomaceous earth, clay, dolomite, calcite, silicon dioxide, china clay/kaolin clay, talc, starch, zinc and its salts (zinc sulphate, zinc oxide, zinc lactate gluconate, zinc polyflavonoid, Zinc EDTA), iron and its salt (ferrous sulphate, Fe EDTA), copper and salts, Sulphur, humic acid and salt, fulvic acid and salt, amino acids, sea weed extracts, chitosan or a combination thereof. It presents in an amount quantity sufficient (QS) required to make 100% w/w formulation.

Coloring agent
The colouring agent/dyes selected from crystal violet, thalocyano dye chlorinated, aerosol green FFB dye, rodamine, azo compound. It present in an amount in the range from 0.1 to 2% w/w.

Controlled release agent
The controlled releasing agent selected from xanthan gum, PVK, carboxymethyl celluloses, polyvinyl alcohols, gelatin, sodium carboxymethyl cellulose, hydroxyethyl cellulose, sodium polyacrylate, modified starch, paraffin wax, polyvinyl acetate, montan wax and vinyl acetate, polyethylene glycol 6000, cationic hydro soluble polymer, C4 alkylated polyvinyl pyrrolidone. It present in an amount in the range from 0.05 to 5% w/w.

The composition may also contain if desired, one or more auxiliary’s customary for crop protection compositions.

The synergistic ternary agrochemical composition comprises of compound (a) Formula I; compound (b) Formula II; compound (c) selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride; and d) one or more inactive excipients.

The process for preparing the present synergistic ternary agrochemical 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 are still covered by the scope of present invention.

While the foregoing written description of the invention enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate the existence of variations, combinations, and equivalents of the specific embodiment, method, and examples herein. The invention should therefore not be limited by the above-described embodiment, method, and examples, but by all embodiments and methods within the scope and spirit of the invention. The invention shall now be described with reference to the following specific examples. It should be noted that the example(s) appended below illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the present invention.

These and other aspects of the invention may become more apparent from the examples set forth herein below. These examples are provided merely as illustrations of the invention and are not intended to be construed as a limitation thereof.

EXAMPLES:
Example 1
Granular (GR) composition of Formula I+Formula II+Thiocyclam hydrogen oxalate
Table 1: Formula I+Formula II+Thiocyclam hydrogen oxalate GR (Granule)
Ingredients Functions FCT-290 FCT-650 FCT-770 FCT-915
Percent (w/w)
Formula I technical (95% purity) Active ingredient 0.42 0.32 0.21 0.16
Formula II technical (98% purity) Active ingredient 0.51 1.22 1.53 2.04
Thiocyclam hydrogen oxalate technical (87.5% purity) Active ingredient 2.29 5.71 6.86 8.00
Alcohol ethoxylate Emulsifier 0.50 0.50 0.50 1.00
Butanol EO/PO copolymer Emulsifier 0.50 0.50 0.50 0.30
Dimethyl sulfoxide Solvent 10.00 10.00 10.00 8.00
Rhodamine Dye 0.20 0.20 0.20 0.30
China clay Inert 6.00 6.00 6.00 8.00
River sand (Silica) Carrier 79.58 75.55 74.20 72.20
Total 100.00 100.00 100.00 100.00

Manufacturing process
Formula I 0.3%+Formula II 1.2%+Thiocyclam hydrogen oxalate 5% GR (FCT-650), 100 kg batch size.
Step 1: Before starting the process, check the cleanliness of all equipment in plant and get approval by QC dept.
Step 2: Check the electrical connection and standardize the weighing balance.
Step 3: Take 10 kg of dimethyl sulfoxide, 0.5 kg of alcohol ethoxylate, 0.5 kg of Butanol EO/PO copolymer and 0.2 kg of Rhodamine dye into a vessel.
Step 4: Now take 75.55 kg of River sand granules into nauta mixture and spray this emulsifier mix solution slowly onto these blank sand granules and homogenize.
Step 5: Add 0.32 kg of Formula I technical, 1.22 kg of Formula II technical and 5.71 kg of Thiocyclam hydrogen oxalate technical and blend on sand granule and mix it till completely homogenize.
Step 6: Finally add 6 kg of China clay to coat the wet granules to make it free flowing.
Step 7: Homogenize it further to get complete homogeneous and free-flowing granules.
Step 8: Transfer these granules to vibro shifter.
Step 9: Collect the final material from the vibro shifter into drum.
Step 10: Finally send the sample to QC for approval and transfer the material into different size of drums.
Storage stability:
The composition was evaluated for its stability. The composition was determined at T0, and under accelerated heat stability (AHS) conditions for 14 days at 54°C designated as T1. The stability was also evaluated after 3 months, at 40°C, designated as T2.
Table 2: Storage stability- Formula I 0.3%+Formula II 1.2%+Thiocyclam hydrogen oxalate 5% GR (FCT-650)
Test parameters T0 (initial) T1 (AHS),for 14 days at 54 0C T2- for three months at 40 0C
Appearance free flowing, free from extraneous matter free flowing, free from extraneous matter free flowing, free from extraneous matter
Formula I content (% w/w, -5% to +10% ) 0.34 0.33 0.33
Formula II content (% w/w, -5% to +10% ) 1.29 1.27 1.27
Thiocyclam hydrogen oxalate content (% w/w, -5% to +10% ) 6.12 6.10 6.10
Dry sieve (%, w/w), >90% 98.80 98.70 98.70
moisture (%, w/w) 0.75 0.74 0.76
dustiness (<20 mg) 8.80 9.00 9.00
pH range (5 to 7, 1% aq. Suspension) 6.70 6.60 6.60

GR formulation of Formula I 0.3%+Formula II 1.2%+Thiocyclam hydrogen oxalate 5% GR (FCT-650) is dry, free flowing granules and meets the required storage stability criteria-active ingredient content, dry sieve test, moisture and dustiness and pH.
Table 3: Granular (GR) composition of Formula I+Formula II+Cartap hydrochloride
Compositions Function FCC-460 FCC-760 FCC-1000 FCC-925
Percent (w/w)
Formula I technical (95% purity) Active ingredient 1.05 0.42 0.21 0.26
Formula II technical (98% purity) Active ingredient 0.61 1.22 1.84 2.04
Cartap hydrochloride technical (98% purity) Active ingredient 3.06 6.12 8.16 7.14
Tri-styryl Phenol Ethoxylate Emulsifier 3.00 3.00 3.00 2.00
Phosphoric acid Buffering agent 0.50 0.50 0.50 0.30
N-methyl-2-pyrrolidone Solvent 3.00 3.00 3.00 2.00
Copolymer of propylene oxide (PO) and ethylene oxide (EO) Dispersing agent 2.50 2.50 2.50 2.00
Rhodamine Dye 0.50 0.50 0.50 0.20
Zinc sulphate monohydrate Inert 2.00 2.00 2.00 1.00
Precipitated silica Inert 1.00 1.00 1.00 5.00
River sand (Silica) Carrier 82.77 79.73 77.29 78.05
Total 100.00 100.00 100.00 100.00

All the recipes (FCC-460, FCC-760, FCC-1000 and FCC-925) of GR formulation of Formula I+Formula II+Cartap hydrochloride are dry, free flowing granules and meets the required storage stability criteria-active ingredient content, dry sieve test, moisture and dustiness and pH.
Example 2
Wettable Powder (WP) composition of Formula I+Formula II+Thiocyclam hydrogen oxalate.
Table 4: Formula I 4%+Formula II 4%+Thiocyclam hydrogen oxalate 40% WP
Ingredients Function Percent (w/w)
Formula I technical (95% purity) Active ingredient 4.21
Formula II technical (98% purity) Active ingredient 4.08
Thiocyclam hydrogen oxalate technical (86% purity) Active ingredient 46.51
Alkyl naphthalene Sulfonate Wetting agent 2.50
Alkyl naphthalene sulfonate (ANS) condensate Dispersing agent 5.00
Citric acid Chelating agent 0.10
Silicon dioxide Anticaking agent 1.00
Poly dimethyl siloxane Antifoaming agent 0.20
Acid green dye Dye 0.10
Zinc oxide Filler 2.00
China clay Filler 34.30
Total 100.00

Example for manufacturing of 100 kg batch of Formula I 4%+Formula II 4%+Thiocyclam hydrogen oxalate 40% WP
Step 1- Charge the required quantity of 34.3 kg of China clay, 2 kg of zinc oxide, 0.2 kg of poly dimethyl siloxane, 1.0 kg of silicon dioxide, 0.10 kg of citric acid, 5.0 kg of alkyl naphthalene sulfonate condensate, 0.1 kg of acid green dye and 2.5 kg of alkyl naphthalene sulfonate in premixing blender for homogenization for 30 minutes.
Step 2-Now add 4.21 kg of Formula I technical, 4.08 kg of Formula II technical and 46.51 kg of Thiocyclam hydrogen oxalate technical and again homogenize for 30 more minutes.
Step 3-Pre-blended material is then 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-Final product is sent for QC approval.
Step 4-After approval material is packed in required pack sizes.

Storage stability
The composition was evaluated for its stability. The composition was determined at T0, and under accelerated heat stability (AHS) conditions for 14 days at 54°C designated as T1. The stability was also evaluated after 3 months, at 40°C, designated as T2.
Table 5: Storage stability-Formula I 4%+Formula II 4%+Thiocyclam hydrogen oxalate 40% WP
Test parameters T0 (initial) T1 (AHS),for 14 days at 54 0C T2- for three months at 40 0C
Formula I content (% w/w, -5% to +10% ) 4.45 4.44 4.44
Formula II content (% w/w, -5% to +10% ) 4.38 4.37 4.37
Thiocyclam hydrogen oxalate content (% w/w, -5% to +5% ) 47.80 47.20 47.30
wettability (60 second, maximum) 14.00 15.00 15.00
suspensibility (minimum 70%) 95.00 94.50 94.50
pH range (6 to 8, 1% aq. Suspension) 6.90 6.80 6.80

WP formulation of Formula I 4%+Formula II 4%+Thiocyclam hydrogen oxalate 40% WP meets the required storage stability criteria-active ingredient content, wettability, suspensibility and pH.
Table 6: Formula I 4%+Formula II 4%+Cartap hydrochloride 45% WP
Ingredients Function Percent (w/w)
Formula I technical (95% purity) Active ingredient 4.21
Formula II technical (98% purity) Active ingredient 4.08
Cartap hydrochloride technical (98% purity) Active ingredient 45.92
Alkyl phenol ethylene oxide Emulsifier 0.70
Isopropyl acid phosphate Wetting agent 0.30
Acid green dye Dye 0.05
4-O-beta-D-galacto pyranosyl-alpha-D-glucophyranose / lactose Filler 44.74
Total 100.00

WP formulation of Formula I 4%+Formula II 4%+Cartap hydrochloride 45% WP meets the required storage stability criteria-active ingredient content, wettability, suspensibility and pH.
Example 3
Wettable Granule (WG) composition of Formula I+Formula II+Cartap hydrochloride.
Table 7: Formula I 5%+Formula II 2%+Cartap hydrochloride 60% WG
Ingredients Functions Percent (w/w)
Formula I technical (95% purity) Active ingredient 5.26
Formula II technical (98% purity) Active ingredient 2.04
Cartap hydrochloride technical (98% purity) Active ingredient 61.22
Alkyl naphthalene sulphonate condensate sodium salt Dispersing agent 7.00
Sodium aromatic aryl sulphonate Wetting agent 3.00
Prussian blue Dye 0.10
Calcium hydroxide Buffering agent 3.00
Polydimethylsiloxane Anti-foaming agent 0.10
China clay Carrier 18.27
Total 100.00

Manufacturing process- Formula I 5%+Formula II 2%+Cartap hydrochloride 60% WG
100 kg batch size.
Step 1-Charge 18.27 kg of China clay, 0.1 kg of polydimethylsiloxane, 3 kg of calcium hydroxide, 7 kg of alkyl naphthalene sulphonate condensate sodium salt, 3 kg of sodium aromatic aryl sulphonate and 0.1 kg of Prussian blue dye in premixing blender for homogenization for 30 minutes.
Step 2-Now add 5.26 kg of Formula I technical, 2.04 kg of Formula II technical and 61.22 kg of cartap hydrochloride technical and again homogenize for 30 more minutes.
Step 3-Pre-blended material is then 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 4-Finely grinded powder is mixed 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 Fluidized 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.

Storage stability:
The composition was evaluated for its stability. The composition was determined at T0, and under accelerated heat stability (AHS) conditions for 14 days at 54°C designated as T1. The stability was also evaluated after 3 months, at 40°C, designated as T2.
Table 8: Storage stability-Formula I 5%+Formula II 2%+Cartap hydrochloride 60% WG
Test parameters T0 (initial) T1 (AHS),for 14 days at 54 0C T2- for three months at 40 0C
Formula I content (% w/w, -5% to +10% ) 5.68 5.67 5.67
Formula II content (% w/w, -5% to +10% ) 2.20 2.19 2.19
Cartap hydrochloride content (% w/w, -5% to +5% ) 62.95 62.90 62.92
wettability (60 second, maximum) 12.0 10.0 10.0
suspensibility (minimum 70%) 96.2 95.4 95.2
pH range (6 to 8, 1% aq. Suspension) 6.5 6.4 6.4

WG formulation of Formula I 5%+Formula II 2%+Cartap hydrochloride 60% WG meets the required storage stability criteria-active ingredient content, wettability, suspensibility and pH.
Table 9: Formula I 5%+Formula II 2%+Thiocyclam hydrogen oxalate 50% WG
Ingredients Functions Percent (w/w)
Formula I technical (95% purity) Active ingredient 5.26
Formula II technical (98% purity) Active ingredient 2.04
Thiocyclam hydrogen oxalate technical (86% purity) Active ingredient 58.14
Di alkyl naphthalene sulphate sodium salt Wetting agent 2.50
Modified Sodium lignosulfonate Dispersing agent 5.00
Ammonium Sulphate Disintegrating agent 8.00
Polydimethylsiloxane Anti-foaming agent 0.50
Lactose Binder 5.00
China clay Carrier 13.56
Total 100.00

Storage stability:
WG formulation of Formula I 5%+Formula II 2%+Thiocyclam hydrogen oxalate 50% WG meets the required storage stability criteria-active ingredient content, wettability, suspensibility and pH.
Example 4
Biological examples
Evaluation of synergistic effect of insecticidal composition of the present invention.
The synergism between two or three pesticidal compounds can be evaluated as per the method given by S R Colby. Calculating Synergistic and Antagonistic Responses of Herbicide Combinations, published online by Cambridge University Press: 12 June 2017, pp. 20-22 (Weeds, Journal of The Weed society of America, Volume 15, January 1967, Issue 1, Page 20-22).

Experiment 1: Synergistic control of paddy stem borer
Crop: Paddy
Plot size: 6 m x 5 m.
Pests: Paddy stem borer, Scirpophaga incertulas
Application Method: The required quantity of granules was manually broadcasted uniformly in the plot on 20th day after transplanting.
Methodology: Paddy stem borer is an internal borer and can destroy rice at any stage of plant from seedling to maturity. Larvae bores into the stem and feeds on internal part of plant which caused dead heart symptoms (drying of central tillers) during vegetative stage and white ear head symptoms (panicles without grains) at reproductive stage. The incidence of dead heart symptoms recorded by counting the number of healthy and infested/dead tillers per hill, observe 20 hills per plot at 15 and 30th day after application (DAA). Calculate dead heart incidence and reduction in dead heart (as control observed) by below given formula.


Productive tiller count: Count the number of productive tillers (with panicles) per spot, record the observations from 10 spots per plot.
Grain yield: Record the grain yield per plot (kg/plot) and convert it into quintal per hectare at the time of harvest.
Table 10: Treatments
S.No. Treatment details Dose per hectare
active Ingredients (g) formulation (g)
T1 Control (Untreated) - -
T2 Formula I 0.7% GR 30 4285.7
T3 Formula I 0.7% GR 22.5 3214.3
T4 Formula I 0.7% GR 15 2142.9
T5 Formula II 0.5% GR 37.5 7500
T6 Formula II 0.5% GR 90 18000
T7 Formula II 0.5% GR 112.5 22500
T8 Thiocyclam hydrogen oxalate 4% GR 150 3750
T9 Thiocyclam hydrogen oxalate 4% GR 375 9375
T10 Thiocyclam hydrogen oxalate 4% GR 450 11250
T11 Formula I 0.3%+Formula II 1.2% GR 22.5+90 7500
T12 Formula I 0.3%+Thiocyclam hydrogen oxalate 5% GR 22.5+375 7500
T13 Thiocyclam hydrogen oxalate 3%+Formula II 1.2% GR 300+120 10000
T14 Chlorantraniliprole 0.5%+Formula II 1%+Thiocyclam hydrogen oxalate 3% GR 50+100+300 10000
T15 Formula I 0.4%+Formula II 0.5%+Thiocyclam hydrogen oxalate 2% GR (FCT-290) 30+37.5+150 7500
T16 Formula I 0.3%+Formula II 1.2%+Thiocyclam hydrogen oxalate 5% GR (FCT-650) 22.5+90+375 7500
T17 Formula I 0.2%+Formula II 1.5%+Thiocyclam hydrogen oxalate 6% GR (FCT-770) 15+112.5+450 7500
T15 to T17-present compositions, T14-known ternary composition, T11 to T13-known binary compositions.

Table 11: Reduction in Dead Heart Incidence (stem borer)
S.No. Reduction (%) in Dead Heart incidence
at 15 DAA at 30 DAA
Observed Expected Ratio Observed Expected Ratio
T1 0.0 - - 0.0 - -
T2 65.8 - - 47.8 - -
T3 50.5 - - 29.7 - -
T4 28.6 - - 12.5 - -
T5 15.7 - - 2.6 - -
T6 36.5 - - 18.6 - -
T7 51.2 - - 31.9 - -
T8 40.6 - - 21.4 - -
T9 61.8 - - 42.6 - -
T10 75.2 - - 59.7 - -
T11 67.8 68.57 0.99 40.3 42.78 0.94
T12 78.5 81.09 0.97 57.8 59.65 0.97
T13 70.4 - - 41.8 - -
T14 95.8 - - 89.3 - -
T15 99.2 82.87 1.20 96.6 60.04 1.61
T16 100.0 87.99 1.14 100.0 67.15 1.49
T17 100.0 91.36 1.09 100.0 75.99 1.32

Table 12: Reduction in White Ear Incidence (stem borer) and grain yield
S.No. Reduction(%) in White Ear incidence Productive tiller count Grain yield (quintal/hectare)
at harvest
Observed Expected Ratio
T1 0.0 - - 180.3 32.5
T2 47.8 - - 231.7 42.7
T3 29.7 - - 227.5 39.4
T4 12.5 - - 213.5 37.2
T5 2.6 - - 194.8 33.8
T6 18.6 - - 205.3 35.9
T7 31.9 - - 210.6 36.5
T8 21.4 - - 208.4 38.5
T9 42.6 - - 218.7 39.6
T10 59.7 - - 230.3 41.8
T11 40.3 42.78 0.94 237.7 42.1
T12 57.8 59.65 0.97 238.8 42.5
T13 41.8 - - 243.3 43.9
T14 84.8 - - 248.8 50.3
T15 95.2 60.04 1.59 284.2 59.5
T16 100.0 67.15 1.49 291.5 61.8
T17 98.8 75.99 1.30 293.9 61.5

The field experiment results show all the present compositions (T15 to T17) provide synergistic as well as residual control of paddy stem borer on 15th and 30th day after application (in terms of reduction in dead heart incidence, Table 11) and at the time of harvest (in terms of reduction in white ear incidence, Table 12). All three present compositions also produce higher number of productive tillers and grain yield (Table 12) as compared to all the binary (T11 to T13) and ternary (T14) prior art combinations.
The visual observations also shows Phyto tonic effect by present compositions (T15 to T17) in rice crop, in terms of increase in greening effect (due to higher chlorophyll), leaf blade size, root biomass and higher number of tillers.

Experiment 2: Synergistic control of paddy stem borer
Crop: Paddy
Plot size: 7 m x 4.5 m.
Pests: Paddy stem borer, Scirpophaga incertulas
Application Method: The required quantity of granules was manually broadcasted uniformly in the plot on 17th day after transplanting.
Methodology: as per experiment 1.

Table 13: Treatment details
S.No. Treatment details Dose per hectare
active Ingredients (g) formulation (g)
T1 Control (Untreated) - -
T2 Formula I 0.7% GR 75 10714.3
T3 Formula I 0.7% GR 30 4285.7
T4 Formula I 0.7% GR 15 2142.9
T5 Formula II 0.5% GR 45 9000
T6 Formula II 0.5% GR 90 18000
T7 Formula II 0.5% GR 135 27000
T8 Cartap hydrochloride 4% GR 225 5625
T9 Cartap hydrochloride 4% GR 450 11250
T10 Cartap hydrochloride 4% GR 600 15000
T11 Formula I 0.4%+Formula II 1.2% GR 30+90 7500
T12 Formula I 0.4%+Cartap hydrochloride 6% GR 30+450 7500
T13 Formula II 1.2%+Cartap hydrochloride 6% GR 90+450 7500
T14 Chlorantraniliprole 0.4%+Cartap hydrochloride 7.5% GR 35+656.25 8750
T15 Chlorantraniliprole 0.5%+Formula II 1%+Cartap hydrochloride 4.5% GR 50+100+450 10000
T16 Formula I 1%+Formula II 0.6%+Cartap hydrochloride 3% GR (FCC-460) 75+45+225 7500
T17 Formula I 0.4%+Formula II 1.2%+Cartap hydrochloride 6% GR (FCC-760) 30+90+450 7500
T18 Formula I 0.2%+Formula II 1.8%+Cartap hydrochloride 8% GR (FCC-1000) 15+135+600 7500
T16 to T18-present compositions, T15-known ternary composition, T11 to T14-known binary compositions.

Table 14: Reduction in Dead Heart Incidence (stem borer)
S.No. Reduction (%) in Dead Heart incidence
at 15 DAA at 30 DAA
Observed Expected Ratio Observed Expected Ratio
T1 0.0 - - 0.0 - -
T2 74.6 - - 60.2 - -
T3 65.7 - - 49.6 - -
T4 29.1 - - 10.8 - -
T5 31.4 - - 16.5 - -
T6 37.2 - - 22.8 - -
T7 48.6 - - 34.5 - -
T8 50.3 - - 36.2 - -
T9 60.5 - - 46.3 - -
T10 73.8 - - 65.5 - -
T11 69.4 78.46 0.88 53.7 61.09 0.88
T12 75.3 86.45 0.87 61.8 72.94 0.85
T13 80.2 - - 64.6 - -
T14 84.6 - - 71.3 - -
T15 91.6 83.8
T16 100.0 91.34 1.09 98.2 78.80 1.25
T17 100.0 91.49 1.09 100.0 79.11 1.26
T18 100.0 90.45 1.11 100.0 79.84 1.25

Table 15: Reduction in White Ear Incidence (stem borer) and grain yield
S.No. Reduction(%) in White Ear incidence Productive tiller count Grain yield (quintal/hectere)
at harvest
Observed Expected Ratio
T1 0.0 - - 167.4 30.12
T2 45.8 - - 210.3 36.98
T3 32.5 - - 203.8 34.70
T4 1.2 - - 195.6 32.70
T5 2.5 - - 198.7 33.30
T6 7.6 - - 203.5 34.50
T7 18.9 - - 214.5 36.70
T8 20.8 - - 217.8 37.80
T9 32.7 - - 228.3 39.50
T10 52.6 - - 239.4 41.30
T11 37.6 37.63 1.00 241.6 41.80
T12 47.3 54.57 0.87 240.5 41.70
T13 50.7 - - 245.3 41.90
T14 56.2 - - 243.5 41.80
T15 67.7 - - 256.3 52.40
T16 95.3 58.15 1.64 295.3 61.20
T17 99.2 58.02 1.71 302.5 62.90
T18 100.0 62.02 1.61 304.3 63.20

The field experiment results show all the present compositions (T16 to and T18) provide synergistic as well as residual control of paddy stem borer on 15th and 30th day after application (in terms of reduction in dead heart incidence, Table 14) and at the time of harvest (in terms of reduction in white ear incidence, Table 15).
All three present compositions (T16 to T18) also produce higher number of productive tillers which are directly contributing to the grain yield. The present compositions will helps the farmer to protect their crop for longer duration and reduce crop protection cost and lower the active ingredients loading into the environment.
The visual observations also show Phyto tonic effect by present compositions (T16 to T18) in rice crop, in terms of increase in greening effect (due to higher chlorophyll), leaf blade size, root biomass and higher number of tillers.

Experiment 3: Residual control of paddy leaf folder (Cnaphalocrosis medinalis)
Crop: Paddy
Plot size: 7 m x 5 m.
Pests: Paddy stem borer, Scirpophaga incertulas
Application Method: foliar spray after leaf folder infestation. The spraying should be done with backpack sprayer using 450 liters of water per hectare.
Methodology: Leaf folder damage (%): Count the number of healthy leaflets and damaged leaflet by leaf folder larvae per hill. Record the observations from 10 hills per plot. Calculate leaf folder damage (%) and thereby reduction in leaf folder damage (%) as per below given formula.



Table 16: Treatment details.
S.No. Treatment details Dose per hectare
active Ingredients (g) formulation (g)
T1 Control (Untreated) - -
T2 Formula I 20% WG 30 60.0
T3 Formula II 50% WG 30 75
T4 Thiocyclam hydrogen oxalate 50% SP 300 600
T5 Cartap hydrochloride 50% SP 337.5 675
T6 Formula I 4%+Formula II 4%+Thiocyclam hydrogen oxalate 40% WP 30+30+300 750
T7 Formula I 4%+Formula II 4%+Cartap hydrochloride 45% WP 30+30+337.5 750
T6 and T7-present compositions.
Table 17: control of paddy leaf folder.
S.No. Reduction (%) in Leaf folder damage
at 7 DAA at 14 DAA
Observed Expected Ratio Observed Expected Ratio
T1 0.0 - - 0.0 - -
T2 68.5 - - 51.6 - -
T3 17.3 - - 4.8 - -
T4 75.2 - - 57.8 - -
T5 73.8 - - 53.4 - -
T6 100.0 93.54 1.07 100.0 80.56 1.24
T7 100.0 93.17 1.07 98.7 78.53 1.26

Both the present compositions (T6 and T7) gave complete protection against paddy leaf folder up to 14th DAA.

Experiment 4: Early shoot borer control in sugarcane.
Crop: Sugarcane
Plot size: 16 m x 5 m.
Pests: Early shoot borer (Chilo infuscatellus)
Application Method: foliar spray
Water volume: 450 liter per hectare
Spray equipment: Backpack sprayer
Methodology:
Early shoot borer (ESB) incidence (%): ESB is an internal borer, damage the sugarcane shoot by boring inside the growing shoots/tillers. The observations on ESB incidence recorded by non-destructive method. Count the number of healthy and infested shoots/tillers from central two rows and calculate ESB incidence (%). Recalculate reduction in ESB incidence as ESB control (%) as per the given formula.

Table 18: Treatment details.
S.No. Treatment details Dose per hectare
active Ingredients (g) formulation (g)
T1 Control (Untreated) - -
T2 Formula I 20% WG 40 80.0
T3 Formula II 50% WG 16 40
T4 Thiocyclam hydrogen oxalate 50% SP 400 800
T5 Cartap hydrochloride 75% SG 480 640
T6 Formula I 5%+Formula II 2%+Thiocyclam hydrogen oxalate 50% WG 40+16+400 800
T7 Formula I 5%+Formula II 2%+Cartap hydrochloride 60% WG 40+16+480 800
T6 and T7-present compositions.
Table 19: Reduction in ESB incidence in sugarcane crop.
S.No. Reduction (%) in Early shoot borer incidence
at 10 DAA at 20 DAA
Observed Expected Ratio Observed Expected Ratio
T1 0.0 - - 0.0 - -
T2 68.3 - - 59.5 - -
T3 15.2 - - 3.2 - -
T4 73.6 - - 60.6 - -
T5 70.2 - - 55.8 - -
T6 100.0 92.90 1.08 96.2 84.55 1.14
T7 100.0 91.99 1.09 93.8 82.67 1.13

Both the present compositions (T6 and T7) provide excellent control of ESB on 10th and 20th days after application (DAA).
, Claims:I/We Claim,
1. A synergistic ternary agrochemical composition comprising:
a. compound (A) N1 -[1,1-dimethyl-2(methyl sulfonyl) ethyl]-3-iodo-N-{4- [1,2,2,2-tetrafluoro-l-trifluoromethyl)ethyl}-0- tolyl}phthalimide, known as Formula I;
b. compound (B) (E)-1(2-chloro-1, 3-thiazol-5-ylmethyl)-3-methyl-2- nitroguanidine, known as Formula II;
c. compound (C) is selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride; and
d. one or more inactive excipients.

2. The synergistic ternary agrochemical composition as claimed in claim 1, wherein Compound (A) Formula I is in amount of 0.1% to 10.0% w/w; compound (B) Formula II is in amount of 0.1% to 10.0% w/w; and compound (C) is selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride is in amount of 1.0% to 75.0% w/w.

3. The synergistic ternary agrochemical composition as claimed in claim 1, wherein one or more inactive excipients is selected from solvent, emulsifier, wetting agent, dispersing agent, antifoaming agent/defoamer, disintegrating agent, dye, chelating agent, binder, anti-caking agent, filler and/or a combination thereof and other additives, if required in a formulation.

4. The synergistic ternary agrochemical composition as claimed in claim 1, wherein the formulation for the said composition is selected from Water dispersible granules/Wettable Granule (WDG/WG), Water soluble granules (SG), Emulsifiable granule (EG), Wettable powder (WP), Water Dispersible Powder (WDP), Soluble powder (SP), Emulsifiable powder (EP), Oil dispersible powder (OP), Soluble Tablet (ST), Granules (GR) for soil application, Controlled (Slow or Fast release) Release Granule (CR-GR).

5. The synergistic ternary agrochemical composition as claimed in claim 4, wherein the Granules (GR) formulation comprises:
i. Compound (A) Formula I present in an amount of 0.1% to 10.0% w/w;
ii. Compound (B) Formula II present in an amount of 0.1% to 10.0% w/w;
iii. Compound (C) is selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride present in an amount of 1.0% to 75.0% w/w;
iv. Emulsifier in an amount of 1.0% to 5.0 % w/w;
v. Dispersing agent in an amount of 1.0% to 10.0% w/w;
vi. Solvent in an amount of 1.0% to 15.0% w/w;
vii. Dye in an amount of 0.1% to 0.5% w/w;
viii. Buffering agent in an amount of 0.1% to 0.5% w/w; and
ix. Carrier & filler are in amount of quantity sufficient.

6. The synergistic ternary agrochemical composition as claimed in claim 4, wherein the Wettable Powder (WP) formulation comprises:
i. Compound (A) Formula I present in an amount of 1.0% to 10.0% w/w;
ii. Compound (B) Formula II present in an amount of 1.0% to 10.0% w/w;
iii. Compound (C) is selected from Thiocyclam hydrogen oxalate or Cartap hydrochloride present in an amount of 1.0% to 75.0% w/w;
iv. Wetting agent in an amount of 0.1% to 5.0 % w/w;
v. Dispersing agent in an amount of 1.0% to 5.0% w/w;
vi. Dye in an amount of 0.02% to 0.1% w/w;
vii. Emulsifier in an amount of 0.1% to 5.0% w/w;
viii. Chelating agent in an amount of 0.01% to 0.2% w/w;
ix. Anticaking agent in an amount of 0.1% to 2.0% w/w;
x. Antifoaming agent in an amount of 0.1% to 5.0% w/w; and
xi. Filler in a quantity sufficient amount.

7. The synergistic ternary agrochemical composition as claimed in claim 4, wherein the Wettable Granule (WG) formulation comprises:
a. Compound (A) Formula I present in an amount of 1.0% to 10.0% w/w;
b. Compound (B) Formula II present in an amount of 1.0% to 10.0% w/w;
c. Compound (C) is selected from Cartap hydrochloride or Thiocyclam hydrogen oxalate present in an amount of 1.0% to 75.0% w/w;
d. Wetting agent in an amount of 1.0% to 5.0 % w/w;
e. Dispersing agent in an amount of 1.0% to 10.0% w/w;
f. Disintegrating agent in an amount of 2.0% to 10.0% w/w;
g. Binding agent in an amount of 0.1% to 5.0% w/w;
h. Antifoaming agent in an amount of 0.1% to 5.0% w/w;
i. Buffering agent in an amount of 0.1% to 4.0% w/w;
j. Dye in an amount of 0.01% to 1.0% w/w; and
k. Carrier is in quantity sufficient amount.

8. The synergistic ternary agrochemical composition as claimed in claims 6 and 7, wherein wetting agent is selected from tristyryl phenol ethoxylate non-ionic polymer, sodium iso propyl naphthalene sulphonate, alkyl phenyl ethoxylate, aryl phenyl ethoxylate, aryl phenyl ether phosphate, alkoxylated alcohol, ethoxylated fatty alcohol, ethylene oxide-propylene oxide (EO-PO) block copolymer, alkyl aryl sulphonate, alkyl olefin sulfonate, dioctyl succinate, sodium lauryl sulfate, alkyl polyglucoside, sodium alkyl aryl taurate, sorbitol esters, sorbitol oleate, poly aryl phenyl ether phosphate, polyalkoxylated butyl ether, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium dodecyl benzene sulfonate, alkyl diphenyl sulfonates, sodium isopropyl naphthalene sulfonate, alkyl naphthalene sulfonate. Ethoxylated alcohol includes natural fatty alcohol (lauryl alcohol ethoxylate, lauryl alcohol alkoxylate), synthetic alcohol ethoxylate (tridecyl alcohol ethoxylate, 2-ethyl hexanol, 2-propylheptanol, isodecyl alcohol, trisiloxane ethoxylate, heptamethyl trisiloxane, modified form includes polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, polyalkyleneoxide modified Tri siloxane, polyalkyleneoxide modified polydimethylsiloxane, may be liquid or powder form or a combination thereof.

9. The synergistic ternary agrochemical composition as claimed in claims 5, 6 and 7, wherein Dispersing agent is selected from the group comprising poly(methyl acrylate), poly(ethyl acrylate), poly(propyl acrylate), poly(n-butyl acrylate), poly(isobutyl acrylate), poly(2-ethyl acrylate), poly(t-butyl acrylate), poly(ethylhexyl acrylate), poly(benzyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate), poly((ethylene glycol) methyl ether methacrylate), poly(methacrylate-coethylacrylate), poly(methacrylate-co-styrene), poly(methacrylate-co-butylmethacrylate), poly(n-butylmethacrylcate-co-methacrylate), poly((ethylene oxide)-co-poly(methyl acrylate)), polymethyl methacrylate-polyethylene glycol graft copolymer (Atlox 4913), nonionic comb-shaped polyacrylate (Dispersogen PSL 100), 2-Acrylamido-2-Methylpropane Sulfonic Acid, Sodium methallyl sulfonate, 3-sulfopropyl acrylate potassium salt, 3-sulfopropyl methacrylate potassium salt, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxymethyl methacrylate, Polyethylene-g-poly(n-butyl acrylate), and the mixtures thereof. Polyarylphenyl ether phosphate, Tri styryl phenol ethoxylate, ethoxylated tristryl phenol sulphate, acrylic polymer amine salt, naphthalene sulfonic acid-sodium salt condensate with formaldehyde, alkylated naphthalene sulfonate-sodium salt, ethoxylated oleylcetyl alcohol, poly alkelene glycol ether, ethoxylated fatty alcohol, alkyl sulfonate, styrene acrylic copolymer, alkyl phenol polyglycol ether, sodium lignosulfonate, calcium lignosulfonate, sodium polycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propylene oxide- polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycol ether-phosphate, tristyrylphenole with 16 moles EO, oleyl-polyglycol ether with ethylene oxide, tallow fatty amine polyethylene oxide, nonylphenol polyglycol ether with 9-10 moles ethylene oxide or a combination thereof.

10. The synergistic ternary agrochemical composition as claimed in claim 5, wherein solvent and co-solvent is selected from demineralized (DM) water, alcohols such as ethanol, propanol, n-octanol, isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, acetophenone, glycerin, polyol ethers such as ethylene glycol monopropyl ether, diethylene glycol, monomethyl ether, Di propylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, isoparaffin, kerosene, mineral oil; heavy aromatic hydrocarbons such as mixture of heavy aromatic naphtha hydrocarbon C-9 to C-16, xylene, toluene, naphthalene, solvent naphtha, solvent C9, solvent C10, solvent C12, solvesso 100, solvesso 150, solvesso 200; carboxamide; aliphatic or aromatic hydrocarbons such as chlorobenzene, chloroethylene, methylene chloride; esters such as ethyl acetate, Di isopropyl phthalate, dimethyl adipate, methyl oleate, methyl tallowate; lactones such as gamma-butyrolactone; alkyl amide, amides such as dimethylformamide, alkyl pyrrolidone, N-methyl-2-pyrrolidone, N-octyl pyrrolidone, N,N-dimethyldecanamide, N, N-dimethyloctanamide, N, N-dimethylamine, N,N-dimethylmethanamide; nitriles such as acetonitrile; organosulfur compound such as alkyl sulfoxide, dimethyl sulfoxide, propylene carbonate, mineral oil, methylated seed oil-methyl ester of palm oil/soybean oil/castor oil/cotton seed oil/blend of two or more seed oil.

11. The synergistic ternary agrochemical composition as claimed in claims 6 and 7, wherein Defoamer/Anti-foaming agent is selected from siloxane polyalkylene oxide, polydimethyl siloxane, polysiloxane emulsion, vegetable oil-based antifoam, silicone oil emulsion, magnesium stearate or a combination thereof.

12. The synergistic ternary agrochemical composition as claimed in claims 5 and 6, wherein Disintegrating agent is selected from inert material such as clays, bentonite, diatomaceous, colloidal silica, kaolin which swell by water absorption improve in dispersibility. Water soluble salts such as potassium phosphate, ammonium sulphate, sodium sulphate, sodium citrate, urea or a combination thereof.

13. The synergistic ternary agrochemical composition as claimed in claim 7, wherein Binding agent is selected from poly ethylene wax, poly vinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene oxide, polyethoxylated fatty acids, polyesters, polyamides, poly carbonates, poly urea, poly urethanes, styrene copolymer, butadiene copolymers, polyethoxylated alcohols, acrylate polymer such as polymethacrylate, poly ethyl methacrylate, poly methyl methacrylate, acrylate copolymers and styrene-acrylic copolymers or mixtures of thereof, a natural gum, lignosulphonate, and a combination thereof. The binder is a water swellable binder selected from a group consisting of China clay, bentonite, fuller’s earth, zeolite, quartz, precipitated silica, palygorskite, sepiolite, halloysite or a combination thereof.

14. The synergistic ternary agrochemical composition as claimed in claims 5 and 6, wherein Emulsifier is selected from castor oil ethoxylate 40 mole, Polyoxyethylenealkylphenyl ether alkyl aryl sulfonate, 3-methoxy N, N-dimethyl propionamide, Polyglyceryl-3 caprylate, Polysorbate 60 (polyoxyethylene sorbitan monostearate-Tween 60), solvents alkyl phenol, aryl phenol, alkyl phenol ethoxylate, fatty acid esters, fatty acid alkanol amides, alkoxylated fatty acid ester or a combination thereof.

15. The synergistic ternary agrochemical composition as claimed in claim 5, 6 and 7, wherein Carrier/Filler selected from the group comprising sand, silica, precipitated silica, bentonite, attapulgite, ceramic, montmorillonite, pumice, sepiolite, diatomaceous earth, clay, dolomite, calcite, silicon dioxide, china clay/kaolin clay, talc, starch, zinc and its salts (zinc sulphate, zinc oxide, zinc lactate gluconate, zinc polyflavonoid), iron and its salt (ferrous sulphate), copper and salts, Sulphur, humic acid and salt, fulvic acid and salt, amino acids, sea weed extracts, chitosan or a combination thereof.
16. Precipitated silica acts as carrier material, absorbing and holding the active ingredient while maintaining a free flowing, easily dispersible powder form, enhancing wettability by improving water contact, and often providing anti-caking properties to prevent clumping, making it crucial for consistent application of the pesticide when mixed with water for spraying on crops.

17. The synergistic ternary agrochemical composition as claimed in claims 5, and 7, wherein Buffering agent is selected from the group comprising polysaccharides such as xanthan gum, sodium carboxymethyl cellulose, hydroxymethyl cellulose, sodium polyacrylate, bentonite clay, attapulgite clay, aluminum magnesium silicate, hydroxy propyl cellulose, polyvinyl alcohols, modifier starch, acacia gum, gelatin or a combination thereof.

18. The synergistic ternary agrochemical composition as claimed in claim 7, wherein Disintegrating agent or inert materials is selected from clays, bentonite, diatomaceous, colloidal silica, kaolin which swell by water absorption improve in dispersibility. Water soluble salts such as potassium phosphate, ammonium sulphate, sodium sulphate, sodium citrate or urea or a combination thereof.

19. The synergistic ternary agrochemical composition as claimed in claim 5, 6 and 7, wherein Dye is selected from crystal violet, thalocyano dye chlorinated, aerosol green FFB dye, rodamine, azo compound.

20. The synergistic ternary agrochemical composition as claimed in claim 7, wherein Anticaking agent is selected from silica/silicone dioxide, calcium silicate, sodium ferrocyanide, Calcium stearate. Anti-caking agents are used to prevent caking, which is the formation of lumps. They also make packaging, transport, flowability, and consumption easier.

21. The synergistic ternary agrochemical composition as claimed in claim 6, wherein Chelating agent is selected from Dimercaprol, Penicillamine, Trientine, Zinc, Deferasirox, Deferiprone, Deferoxamine, EDTA, Succimer or their combinations thereof.

Dated this 25th day of February 2025