Description:FIELD OF THE INVENTION:

The present invention relates to a synergistic ternary herbicidal composition. More specifically, the present invention relates to herbicidal composition comprising Compound A: N-(2,6-dichlorophenyl)-5-ethoxy-7-fluoro-[1,2,4] triazolo[1,5-c]pyrimidine-2- sulfonamide, known as Formula I, Compound B: N-{2,4-Dichloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]phenyl}methanesulfonamide, known as Formula II, Compound C: selected from Pyroxasulfone or Pendimethalin; and one or more inactive excipients. The present invention further relates to process of preparing said composition and its use as herbicide.

BACKGROUND OF THE INVENTION:

Patent Application Number: 202141050386: The present invention relates to novel herbicidal composition for protecting crops against weeds, undesired vegetation and grasses. More, particularly, the present invention relates to herbicidal composition comprising a mixture of pyroxasulfone, chlorimuron ethyl and diclosulam. The present invention further relates to a method of controlling weeds comprising applying a composition of the present invention to the weeds or an area in need of weed control.

Patent Number: 476861: The present invention discloses a novel formulation of Pendimethalin and Diclosulam and process of preparation thereof, wherein the said composition is in dry flowable form comprising: Pendimethalin Technical in the range of 20-75% w/w, Diclosulam Technical in the range of 0.5-4.0 % w/w, Surfactant in the range of 1-10% w/w, Dispersing agent in the range of 1-8% w/w and Fillers or adjuvants. The present invention more particularly discloses a novel formulation of Pendimethalin and Diclosulam and process of preparation thereof which is easily dispersible in water, eco-friendly, safe to handle, decreases inhalation toxicity, cost-effective and effective against a broad spectrum of weeds.

Application number: 202411065483: A synergistic emulsifiable concentrate composition with widened spectrum of action on plurality of weeds comprising a bio-effective synergistic amount of active Pendimethalin in an amount ranging from 10.0 % to 20.0 % weight percent ratio with respect to said concentrate and Sulfentrazone in a bio-effective synergistic amount ranging from 5.0 % to 15.0 % weight percent ratio with respect to said concentrate, along with particular agriculturally acceptable adjuvants in particular amounts. The present invention is also related to a process for the preparation of said synergistic Emulsifiable concentrate composition.

Application number: 202341080514: The present invention relates to a kind of synergistic herbicide composition that contains herbicidal active compounds, and it is suitable for preventing unwanted plants in the crops like soybean, paddy rice and sugarcane.

Application number: 202021012142: The present invention provides a co-crystal of sulfentrazone and a triazinone herbicide and process for preparation thereof. The present invention also provides an agrochemical composition comprising said co-crystal and process of preparation of an agrochemical composition and method of controlling weeds with said compositions.

Application number: 202021046329: The present disclosure discloses a composition for the protection of plants. More specifically, the present disclosure relates to an herbicidal composition comprising 3-[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)pyrazol-4-ylmethylsulfonyl]-4,5-dihydro-5,5-dimethyl-1,2-oxazole; at least one sulfonylurea herbicide; and at least one additional herbicide. The invention further relates to formulations and methods of controlling undesired plants with the composition.

Application number: 202021052425: The present invention relates to a composition comprising a synergistic combination of herbicide compound [5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl 4,5-dihydro-5,5-dimethylisoxazol -3-yl sulfone; with a herbicide compound 4-amino-6-tert-butyl-3-methylsulfanyl-1,2,4-triazin-5-one; and at least one additional herbicide compound for controlling wide array of weeds growing amongst crop plants. The invention further relates to formulations and methods of controlling undesired plants with the composition.

Formula I is a triazolopyrimidine sulfonamide herbicide developed by Dow AgroSciences LLC in the United States. It is registered under CAS number 145701-21-9. Its chemical name is N-(2,6-dichlorophenyl)-5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide. Formula I is primarily used for pre-plant soil treatment in soybean and peanut fields to prevent and control broadleaf weeds. Its rapid metabolism in the soil ensures safety for soybeans and peanuts, as it converts into inactive compounds.

Formula II, chemical name is N-{2,4-Dichloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]phenyl}methanesulfonamide, is a broad-spectrum herbicide. It functions by inhibiting the enzyme protoporphyrinogen oxidase. Initially introduced in the United States in 1997 by FMC Corporation. It causes visible effects on plants such as chlorosis and desiccation. These symptoms result from the accumulation of protoporphyrin IX in plant cells due to enzyme inhibition. Protoporphyrin IX acts as a powerful photosensitizer, activating oxygen and triggering lipid peroxidation. This process, which requires both light and oxygen, ultimately destroys the plant.

Pyroxasulfone is a pre-emergence herbicide that inhibits the synthesis of very long-chain fatty acids in plants. Its development was inspired by the structure of the herbicide thiobencarb, but pyroxasulfone is more efficient, requiring lower doses (100–25 g/ha) and offering greater stability, resulting in prolonged efficacy. By 2016, it had been approved for use in countries including Japan, Australia, the USA, Canada, Saudi Arabia, and South Africa, and was applied to crops such as maize, soybeans, wheat, and cotton. In 2015, pyroxasulfone was used on over 6 million hectares of farmland.
Although belonging to a novel chemical class, pyroxasulfone shares a similar mode of action with acetamide herbicides like metolachlor, acetochlor, and dimethenamid. It is primarily used to control annual grasses but also effectively targets broadleaf weeds, including lambsquarters (Chenopodium berlandieri), pigweed and waterhemp (Amaranthus species), and black nightshade (Solanum nigrum).

A dinitroaniline class of herbicides “N-(1-Ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine” (Pendimethalin), is a selective herbicide which acts as a cell division inhibitor by inhibiting microtubule assembly. The structure can be represented as:

Pendimethalin is a selective herbicide, absorbed by the roots and leaves. Affected plants die shortly after germination or following emergence from the soil. Pendimethalin is used to control of most annual grasses and many annual broad leaf weeds at 0.4- 2.0 kg a.i./ha in cereals, onions, leeks, garlic, fennel, maize, sorghum, rice, soya beans, peanuts, brassicas, carrots, celery, black salsify, peas, field beans, lupins, evening primrose, tulips, potatoes, cotton, hops, pome fruit, stone fruit, berry fruit (including strawberries), citrus fruit, lettuce, aubergines, capsicums, established turf, and in transplanted tomatoes, sunflowers, and tobacco, applied pre-plant incorporated, pre-emergence, pre-transplanting, or early post-emergence. Also, Pendimethalin is used for control of suckers in tobacco. Pendimethalin is used for weed control management for numerous major crops such as rice, wheat, maize and soybean as well as minor crops such as fruits and vegetables.

Herbicide compositions typically consist of an active ingredient that targets specific weeds, 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 weeds by 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 spreadability of the herbicide, or fragrances to mask odours. The precise combination of these compounds is designed to optimize both the potency and safety of the herbicide, ensuring effective weed control while minimizing risks to humans, animals, and the environment.

In general use, the herbicides actives are used in the form of a dilute aqueous composition because it can attain a good interaction with the target weed. However, most active herbicide compounds that are used as herbicides 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 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 herbicidal activity through synergistic interactions among its compounds yet be simple to produce without requiring complex or resource-intensive production methods.

Therefore, there still exists a need to develop synergistic herbicidal composition, which is stable, synergistic, more effective in control of wide spectrum of weed flora in crop and environmentally safe.

Another objective of the present invention is to provide a synergistic herbicidal composition one-shot formulation effective for controlling undesired weeds.

Yet another objective of the present invention is to provide a synergistic herbicidal 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 herbicidal composition comprising the active ingredients of the present invention and excipients suitable for such composition.

Therefore, an aspect of the present invention is to provide novel synergistic herbicidal composition comprising compound (a) Formula I; compound (b) Formula II; compound (c) selected from Pyroxasulfone or Pendimethalin; 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 hherbicidal composition comprising compound (a) Formula I; compound (b) Formula II; compound (c) selected from Pyroxasulfone or Pendimethalin; and d) one or more inactive excipients with suitable formulation 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 herbicidal composition comprising:
a. Compound (A) Formula I (N-(2,6-dichlorophenyl)-5-ethoxy-7-fluoro-[1,2,4] triazolo[1,5-c]pyrimidine-2- sulfonamide);
b. Compound (B) Formula II (N-{2,4-Dichloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]phenyl}methanesulfonamide);
c. Compound (C) selected from Pyroxasulfone or Pendimethalin; and
d. One or more inactive excipients.

Another aspect of the present invention to provide synergistic herbicidal composition comprises: Compound (A) Formula I is in amount of 0.2% to 10% w/w; compound (B) Formula II is in amount of 5% to 50% w/w; and compound (C) is selected from Pyroxasulfone or Pendimethalin is in amount of 5% to 30% w/w.

Another aspect of the present invention to provide one or more inactive excipients is selected from the group comprising of 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.

Yet another aspect of the present invention is the preparation of formulation for the synergistic herbicidal composition of the present invention is formulated as Water dispersible granules (WDG/WG), Water soluble granules (SG), Emulsifiable granule (EG), Wettable powder (WP), Soluble powder (SP), Emulsifiable powder (EP), Oil dispersible powder (OP), Soluble Tablet (ST), Capsule suspension/Micro capsule (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion water-in-oil (EO), Emulsion oil-in-water (EW), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Suspo Emulsion (SE), Soluble Liquid/Concentrate (SL), mixed formulation of CS and SC (ZC), mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

Further aspect of the present invention is to provide synergistic, broad-spectrum control of harmful weeds.

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.

The present invention relates a synergistic herbicidal composition comprising:
a. Compound (A) Formula I;
b. Compound (B) Formula II;
c. Compound (C) is selected from Pyroxasulfone or Pendimethalin; and
d. One or more inactive excipients.

Another aspect of the present invention to provide a synergistic herbicidal composition comprises: Compound (A) Formula I is in amount of 0.2% to 10% w/w; compound (B) Formula II is in amount of 5% to 50% w/w; and compound (C) is selected from Pyroxasulfone or Pendimethalin is in amount of 5% to 30% w/w.

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

The synergistic herbicidal composition of the present invention is formulated as Water dispersible granules (WDG/WG), Water soluble granules (SG), Emulsifiable granule (EG), Wettable powder (WP), Soluble powder (SP), Emulsifiable powder (EP), Oil dispersible powder (OP), Soluble Tablet (ST), Capsule suspension/Micro capsule (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion water-in-oil (EO), Emulsion oil-in-water (EW), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Suspo Emulsion (SE), Soluble Liquid/Concentrate (SL), mixed formulation of CS and SC (ZC), mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

The synergistic herbicidal composition of present invention controls all kind of monocots, dicots and sedges weeds. The present synergistic herbicidal combinations also control annual and perennial weeds. The most common weeds controlled by present inventions are Abutilon indicum, Acalypha indica, Acanthospermum hispidum, Achyranthes aspera, Aerva tomentosa, Ageratum conyzoides, Alhagi camelorum, Amaranthus hybridus, Amaranthus spinosus, Amaranthus viridis, Ammannia baccifera, Anagallis arvensis, Argemone mexicana, Artemisia nilagiricia, Asphodelus tenuifolius, Avena fatua, Avena ludoviciana, Bidens pilosa, Boerhaavia diffusa, Boerhavia repanda, Brachiaria mutica, Brassica kaber, Bromus tectorum, Calotropis gigantea, Cannabis sativa, Carthamus axyacantha, Cassia tora, Celosia argentea, Centella asiatica, Chenopodium album, Chenopodium murale, Chloris barbata, Chrozophora rottlerii, Cichorium intybus, Cirsium arvense, Clitoria ternatea, Cnicus arvensis, Commelina benghalensis, Commelina communis, Convolvulus arvensis, Conyza canadensis, Corchorus acutangulus, Coronopus didymus, Crotalaria serice, Cucumis callosus, Cuscuta campestris, Cuscuta chinensis, Cynodon dactylon, Cyanotis axillaris, Cyperus esculenthus, Cyperus iria, Cyperus rotundus, Dactyloctenium aegyptium, Datura stramonium, Daucus carota, Digera arvensis, Digitaria sanguinalis, Dinebra retroflexa, Echinochola colonum, Echinochola crusgalli, Eclipta alba, Eichhornia crassipes, Elephantopus scaber, Eleusine indica, Eragrostis major, Euphorbia geniculata, Euphorbia hirta, Fimbristylis miliacea, Fumaria indica, Gynandropsis gynandra, Heliotropium indicum, Indigofera glandulosa, Ipomea aquatica, Lantana camara, Lathyrus aphaca, Launaea asplenifolia, Launaea nudicaulis, Leucas aspera, Ludwigia parviflora, Marsilea quadrifoliata, Medicago denticulate, Mimosa pudica, Melilotus alba, Melilotus indica, Ocimum canum, Oenothera biennis, Opuntia dillenil, Orobanche ramosa, Oryza longistaminata, Oryza sativa, Oxalis corniculata, Oxalis latifolia, Parthenium hysterophorus, Paspalum sanguinale, Phalaris minor, Phyllanthus niruri, Physalis minima, Polypogon monspeliensis, Portulaca oleracea, Prosopis juliflora, Rumex dentatus, Saccharum spontaneum, Stearia glauca, Seteria viridis, Sida spinosa, Silene antirrhina, Sisymbrium irio, Solanum nigrum, Solanum surattense, Sonchus oleraceous, Sorghum halepense, Spergula arvensis, Sphenocleazeylanica Gaertn, Striga asiatica, Tagetes minuta, Trianthema monogyna, Trianthema portulacastrum, Tribulus terrestris, Trigonelia polycerata, Vernonia cinerea, Vicia sativa and Xanthium strumarium.

Crops are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

The synergistic herbicidal compositions are used to controlled unwanted weeds in crops like Sugarcane (Saccharum officinarum), Soybean (Glycin max), Groundnut/Peanut (Arachis hypogaea), orchards (mango, grape, coconut, Chiku, pomegranate, banana), plantation (tea, pineapple) and non-crop land areas.

The synergistic herbicidal compositions are applied as a spraying over the soil, as pre-emergence (after crop sowing and before weed germination), pre plant incorporation (before crop sowing by incorporating into the soil). The application (spraying) can be done by manually or battery-operated backpack sprayer, spray machines, tractor operated sprayer, UAV arial application (example drone).

The synergistic herbicidal composition of specific active ingredients has the special advantage of being highly active against weed flora. The inventors believe that the present invention surprisingly results in a strong synergistic action, allows broad spectrum control of weeds along residual control. The broad-spectrum action of the present invention also provides a solution for preventing the development of resistance.

Active Ingredients Compound A Compound B Compound C
Formula I Formula II Pyroxasulfone or Pendimethalin
% of active ingredients (w/w) 0.2 to 10 5 to 50 5 to 30

Further, synergistic herbicidal compositions comprising compound (A) Formula I; compound (B) Formula II; compound (C) is selected from Pyroxasulfone or Pendimethalin; and d) one or more inactive excipients.

In further aspect the present invention relates to synergistic herbicidal composition comprising compound (A) Formula I is in amount of 0.2% to 10% w/w, preferably 0.6% to 5% w/w; compound (B) Formula II is in amount of 5% to 50% w/w, preferably 9% to 45% w/w; and compound (C) selected from Pyroxasulfone or Pendimethalin is in amount of 5% to 30% w/w, preferably 6% to 27% w/w.

The composition of the present invention comprises agriculturally acceptable excipients selected from the group comprising of 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 acrylic graft copolymer, examples are 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), poly acrylate copolymer.; polyarylphenyl ether phosphate, Tri styryl phenol ethoxylate, ethoxylated tristyryl phenol sulphate, acrylic polymer amine salt, naphthalene sulfonic acid-sodium salt condensate with formaldehyde, alkylated naphthalene sulfonate-sodium salt, ethoxylated oleylcetyl alcohol, polyalkelene 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 alkylaryl sulfonate, 3-methoxy N, N-dimethyl propionamide, Polyglyceryl-3 caprylate, Polysorbate 60 (polyoxyethylene sorbitan monostearate-Tween 60), solventsoalkyl 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.

Anti-foaming agent
Antifoaming agent is generally added to the composition to prevent foam formation as the foam prevents the efficient filling of a container. Suitable defoamer used herein, but not limited to, siloxane polyalkylene oxide, polydimethyl siloxane, polysiloxane emulsion, vegetable oil-based antifoam, silicone oil emulsion, magnesium stearate or a combination thereof and present in an amount in range from 0.01 to 5% w/w.

Anti-freezing agent
An anti-freezing agent is generally added to the composition, to prevent the aqueous compositions from freezing. Suitable anti-freezing agents useful herein, but not limited to ethylene glycol, propane diols, glycerin or the urea, glycol (monoethylene glycol, diethylene glycol, polypropylene glycol, polyethylene glycol), glycerin, urea, magnesium sulfate heptahydrate, sodium chloride etc. The anti-freezing agent is present in an amount in the range from 0.1 to 10% w/w.

Preservative
Preservative is added to the composition for its preservation against spoilage from bacteria, yeasts and fungi. Suitable biocides useful herein, but not limited to, include benzisothiazolin-3-one, formaldehyde, sodium benzoate, sodium o-phenyl phenate, potassium sorbate, 2-bromo-2-nitropropane-1,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one or a combination thereof, and is present in an amount in the range from 0.01 to 1% w/w.

Thickening agent/Suspending agents.
Thickener and suspending agents are typically the same type of substance, usually a high molecular weight polymer, used to increase the viscosity of liquid formulation, preventing solid particles from settling out and ensuring stable suspension, allowing for even distribution when sprayed. The synergistic composition comprises a thickener selected from the group comprising natural polymers (gelling agent): polysaccharides such as xanthan gum, guar gum, acacia gum, gelatin; cellulose derivatives: Carboxymethylcellulose (CMC), hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), sodium carboxymethyl cellulose; clays & minerals: bentonite clay, attapulgite clay, sodium polyacrylate, aluminum magnesium silicate, or a combination thereof and is present in an amount in the range from 0.01 to 5% 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, 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 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, calcium carbonate, 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.

Common stabilizers used in dispersion concentrates include polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose sodium (NaCMC), sodium dodecyl sulphate (SDS), lecithin, polysorbates, and various types of gums like xanthan gum or guar gum; the specific choice depending on the desired properties and application of the dispersion concentrate. Stabilizer used in dispersion concentrate are present in an amount in the range from 1 to 40% 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.

Wall forming material
Capsule suspension (CS) or microcapsule technology that uses membrane forming wall material to embed the core materials that needs to be protected to form tiny particles, which can protect the core material from adverse environment and effectively plays its biological active functions. The wall forming material/ capsule making monomers may be selected from Tetramethylene diisocyanate, Penta methylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4,4-diphenylmethene diisocyanate (MDI), polymethylene polyphenylene isocyanate, 2,4,4’-diphenyl ether tri-isocyanate, 3,3’-dimethyl-4,4’-diphenyl diisocyanate, 3,3’-dimethoxy-4,4’-diphenyl diisocyanate, 1,5-naphthylene diisocyanate and 4,4’4"-triphenylmethane tri-isocyanate, toluene diisocyanate or polymethylene polyphenylisocyanate, polyurethane comprising of polyfunctional iso cyanate and a polyamine in polarized form;, Diethylene triamine, Ammonia, hexamine, ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetra ethylene pentaamine, pentaethylenehexamine, 4,9-dioxadodecane-1, 12-diamine, 1,3- phenylenediamine, 2,4- and 2,6-toluenediamine and 4,4’-diaminodiphenylmethane, 1,3-phenylenediamine, 2,4- and 2,6-toluenediamine, 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 1,3,6-triaminonaphthalene, 2,4,4′-triaminodiphenyl ether, 3,4,5-triamino-1,2,4-triazole and 1,4,5,8-tetraminoanthraquinone. It presents in an amount in the range from 0.1 to 5% w/w.

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), 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. It presents in an amount quantity sufficient (QS) required to make 100% w/w formulation.
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.

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

The synergistic herbicidal composition comprises of compound (A) Formula I; compound (B) Formula II; compound (C) is selected from Pyroxasulfone or Pendimethalin; and d) one or more inactive excipients.

The present synergistic herbicidal composition provides the following advantages:
• Increased efficacy than their individual counterparts or their mixtures, thus allows a substantial reduction in the application rates of each of these active ingredients, while maintaining good efficacy and thereby reducing costs and residue problems.
• The present compositions provide an improved and extended wide spectrum control of unwanted weeds, reduced herbicide application rates and costs, less stringent use restrictions, and improved selectivity.
• Delays the emergence of resistant species.
• Minimizes risk of development of resistance and achieves effective and economical control of undesired vegetation.
• Economically beneficial to the farmers as it provides better yield of the crop.
• Reduced possibility of hazards to the farmers due to occupational exposure because of reduction in the number of sprays.
• Non phytotoxic and safe to the crops.
• Environment friendly.

The process for preparing the present synergistic herbicidal 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
Preparation of composition of Formula I, Formula II and Pyroxasulfone in Wettable Granule (WG) form.
Step 1: weighing the raw materials according to the batch size as follows:
Fillers, dispersing agent, wetting agent, Formula I technical, Formula II technical and pyroxasulfone technical, disintegrating agent, defoamer.
Weigh all these row materials in a pre-blender and mix it for 1 hr.
Step 2: Milling the sample through air jet mill instrument at inlet pressure 2 to 3 kg/cm2 grinding pressure 6 kg/cm2 and checking the particle size <12 micron;
Step 3: Collecting the milled material and post blending the sample for 1 hr.;
Step 4: Extruding the granule @ 35 rpm (1.0 mesh);
Step 5: Collecting the granules and dry the sample at 45 ‘C for 30 min. The moisture content in the dried granules should be below 3.0% by mass.
Step 6: Sending the sample to the quality analysis;
Step 7: Packing the formulated material in suitable packaging.

Table 1: Formula I 2.5%+Formula II 30%+Pyroxasulfone 12.5% WG (Wettable Granule)
Ingredients Function Percent (w/w)
Formula I technical (94% purity) Active Ingredient 2.66
Formula II technical (95% purity) Active Ingredient 31.58
Pyroxasulfone technical (95% purity) Active Ingredient 13.16
Polyacrylate polymer sodium salt Dispersing agent 3.00
Sodium lignosulfonate Dispersing agent 7.00
Dialkyl naphthalene sulphonate sodium salt Wetting agent 2.50
Polydimethyl siloxane Antifoaming agent 1.00
Sodium sulphate anhydrous Disintegrating agent 10.00
Corn starch Carrier/filler 5.00
China Clay (Kaolin) Carrier/filler 24.10
Total 100.00

Preparation of 100 kg composition of Formula I 2.5%+Formula II 30%+Pyroxasulfone 12.5% WG (Wettable Granule)
Step 1-Charge 24.10 kg of China clay, 1 kg of polydimethyl siloxane, 10 kg of sodium sulphate anhydrous, 3 kg of polyacrylate polymer sodium salt, 7.0 kg of sodium lignosulfonate, 2.5 kg of Dialkyl naphthalene sulphonate sodium salt and 5 kg of corn starch in premixing blender for homogenization for 30 minutes.
Step 2-Now add 2.66 kg of Formula I technical, 31.58 kg of Formula II technical and 13.16 kg of pyroxasulfone 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-Formula I 2.5%+Formula II 30%+Pyroxasulfone 12.5% WG
The composition of Formula I 2.5%+Formula II 30%+Pyroxasulfone 12.5% WG 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 of Formula I 2.5%+Formula II 30%+Pyroxasulfone 12.5% WG
Parameters T0 T1 (AHS),for 14 days at 54 'C. T2-3 months at 40 'C
Formula I content (%) (-5% to +10% range) 2.85 2.83 2.81
Formula II content (%), (-5% to +5% range) 32.82 32.75 32.62
Pyroxasulfone content (%) (-5% to +5% range) 13.65 13.62 13.54
suspensibility (minimum 70%) 95.2 94.8 94.6
pH range (6 to 8, 1% aq. Suspension) 7.1 7.1 7.1
wettability (60 second, maximum) 10 10 10

The composition of Formula I 2.5%+Formula II 30%+Pyroxasulfone 12.5% WG 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. The storage stability parameters of actives ingredients content, suspensibility of composition, pH range and wettability were maintained at AHS conditions (T1) and at condition of 40’C for 3 months (T2).

Example 2
Table 3: Formula I 3%+Formula II 25%+Pyroxasulfone 10% WG (Wettable Granule)
Ingredients Function Percent (w/w)
Formula I technical (94% purity) Active Ingredient 3.19
Formula II technical (95% purity) Active Ingredient 26.32
Pyroxasulfone technical (95% purity) Active Ingredient 10.53
Phenol sulfonic acid formaldehyde-polycondensation as sodium salt Dispersing agent 5.00
Acrylate copolymer Dispersing agent 10.00
Alkyl naphthalene sulfonate condensate blend Wetting agent 5.00
Sodium sulphate Disintegrating agent 10.00
Polydimethyl siloxane Antifoaming agent 3.00
Lactose monohydrate Carrier 29.96
Total 100.00

The storage stability study of Formula I 3%+Formula II 25%+Pyroxasulfone 10% WG shows that all the required parameters of actives ingredients, suspensibility of composition, pH range and wettability maintained at AHS conditions (T1) and at condition of 40’C for 3 months (T2).

Example 3
Table 4: Formula I 1.25%+Formula II 43.75%+Pyroxasulfone 18.75% WG (Wettable Granule)
Ingredients Function Percent (w/w)
Formula I technical (94% purity) Active Ingredient 1.33
Formula II technical (95% purity) Active Ingredient 46.05
Pyroxasulfone technical (95% purity) Active Ingredient 19.74
Sodium polycarboxylate Dispersing agent 2.50
Sodium Methyl Oleoyl Taurate Dispersing agent 2.50
Linear Alcohol Derivative Wetting agent 4.50
Ammonium sulphate Disintegrating agent 8.00
Polydimethyl siloxane Antifoaming agent 3.00
Calcium carbonate Carrier 15.38
Total 100.00

The storage stability study of Formula I 1.25%+Formula II 43.75%+Pyroxasulfone 18.75% WG shows that all the required parameters of actives ingredients, suspensibility of composition, pH range and wettability maintained at AHS conditions (T1) and at condition of 40’C for 3 months (T2).

Example 4
Preparation of composition of Formula I, Formula II and pendimethalin in Suspo Emulsion (SE) form:
Weighing the raw materials according to the batch size as follows:
Solvent, emulsifier, biocide, thickener, wetting agent, dispersing agent, suspending agent, anti-freezing agent, buffering agent, technical and defoamer.
Step 1: Gel Solution preparation: Demineralized (DM) water and biocide were taken and homogenized. To it, thickener was slowly added and stirred till completely dissolved to form a solution. This thickener solution was made 12 to 18 hours prior to use.
Step 2: EC premix: Charge solvent and emulsifier into a vessel and then add required quantity of technical and mix till it gets completely homogenized.
Step 3: SC Premix: Charge the required quantity of DM water into a designated vessel for Suspension concentrate production.
Add dispersing agents, wetting agents, anti-freezing agent; and homogenize the contents for 45 to 60 minutes using high shear homogenizer.
Add the required quantity of technical, suspending agents into this premix and homogenize for 30 to 45 minutes.
Before grinding, add required quantity of antifoam and then material was subjected to grinding in Dyno mill till desired particle size is achieved.
Now add remaining quantity of antifoam after milling to avoid foaming.
Step 4: SE formulation: Charge SC premix into other vessel and then add EC premix into SC and homogenize slowly to avoid phase change and finally add gel solution.
Step 5: Quality check and packing.

Table 5: Formula I 0.75%+Formula II 10%+Pendimethalin 25% SE (Suspo Emulsion)
Ingredients Function Percent (w/w)
Formula I technical (94% purity) Active Ingredient 0.80
Formula II technical (95% purity) Active Ingredient 10.53
Pendimethalin technical (90% purity) Active Ingredient 27.78
Dimethylformamide Solvent 4.00
Aromatic solvent (solvent naphtha) Co-Solvent 10.00
Octyl phenol ethoxylate Emulsifier 8.00
Castor oil ethoxylate 40 moles Emulsifier 3.00
Acrylic graft copolymer (2-Propenoic acid, 2-methyl-, polymer with .alpha.-methyl-.omega.-hydroxypoly(oxy-1,2-ethanediyl) and methyl 2-methyl-2-propenoate, graft ) Dispersing agent 2.00
Tristyryphenole with 16 moles EO Dispersing agent 3.00
Copolymer butanol EO/PO (Polyethylene-polypropylene glycol monobutyl ether) Wetting agent 1.50
Attapulgite clay Suspending agent 1.00
Polydimethyl siloxane Antifoaming agent 0.30
1,2- benzisothiazoline-3-one Preservative 0.15
1,2-Propylene glycol Antifreezing agent 5.00
Xanthan gum Thickener 0.15
Water Diluent Water 22.79
Total 100.00

Preparation of 100 kg composition of Formula I 0.75% + Formula II 10% + Pendimethalin 25% SE (Suspo Emulsion)
Weighing the raw materials according to the batch size as follows:
Step 1: Preparation of gum solution: Dissolve 1.5 kg of 1,2-benzisothiazolin-3(2H)-one into 97 kg of Demineralized (DM) water. Now add 1.5 kg of 1,2-Propylene glycol slowly and stir till completely dissolved to form a solution. This gum solution was made 12 to 18 hours prior to use.
Step 2: EC premix: Add 10 kg of solvent naphtha, 4 kg of dimethylformamide, 8 kg of octyl phenol ethoxylate and 3 kg of castor oil ethoxylate 40 moles into other vessel having slow stirring. Add 27.78 kg of pendimethalin technical and mix it properly for 30 to 45 minutes.
Step 3: SC Premix: Charge 12.79 kg of DM water and 5 kg of propylene glycol into designated vessel and mix thoroughly.
Add 1 kg of attapulgite clay, 2 kg of acrylic graft copolymer 9(2-Propenoic acid, 2-methyl-, polymer with .alpha.-methyl-.omega.-hydroxy poly (oxy-1,2-ethanediyl) and methyl 2-methyl-2-propenoate, graft ), 3 kg of Tristyrylphenole with 16 moles EO, 1.5 kg of Copolymer butanol EO/PO (Polyethylene-polypropylene glycol monobutyl ether) and 0.15 kg of polydimethyl siloxane into the vessel and homogenize the mixture for 45 to 60 minutes using high shear homogenizer.
Add 10.53 kg of Formula II tech. and 0.8 kg of Formula I technical to this premix slowly and homogenized to get uniform slurry ready for grinding.
Before grinding, add 0.15 kg of polydimethyl siloxane and do grinding process in Dyno mill till desired particle size achieved.
Step 4: Preparation of SE formulation: Now add EC premix slowly into this milled slurry using slow stirring and homogenize the mixture for 30 to 45 minutes.
Finally add 10 kg of gum solution to this formulation.
Step 5: Collect the sample quality check and packing.

Storage stability study of Formula I 0.75%+Formula II 10%+Pendimethalin 25% SE (Suspo Emulsion):
The composition of Formula I 0.75%+Formula II 10%+Pendimethalin 25% SE 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 three months, at 40°C, designated as T2.

Table 6: Storage stability of Formula I 0.75% + Formula II 10% + Pendimethalin 25% SE (Suspo Emulsion):
Parameters T0 T1 (AHS),for 14 days at 54 'C. T2- for three months at 40 'C
Formula I content (%) (-5% to +10% range) 0.85 0.84 0.84
Formula II content (%), (-5% to +5% range) 10.98 10.95 10.94
Pyroxasulfone content (%) (-5% to +5% range) 28.45 28.43 28.41
suspensibility (minimum 80%) 98.5 98.2 98
pH range (5 to 7, 1% aq. Suspension) 6.4 6.3 6.3
pourability (95% minimum) 98 97.5 97
Viscosity at spindle no. 62, 20 rpm (350 to 800 cps) 650 660 675

The storage stability parameters of actives ingredients content, suspensibility of composition, pH range, pourability and viscosity were maintained at AHS conditions (T1) and at condition of 40’C for 3 months (T2).

Example 5
Preparation of composition of Formula I, Formula II and Pyroxasulfone in Suspension Concentrate (SC) form:
Weighing the raw materials according to the batch size as follows:
Solvent, biocide, thickener, wetting agent, dispersing agent, anti-freezing agent, technical, filler and defoamer.
Step 1: Demineralized (DM) water and biocide were taken and homogenized. To it, thickener was slowly added and stirred till completely dissolved to form a solution. This thickener solution was made 12-18 hours prior to use.
Step 2: Required quantity of DM water was taken in a vessel. Wetting agent, dispersing agent, anti-freezing agent were added and homogenized for 45 to 60 minutes using high shear homogenizer.
Step 3: Then Acetamiprid tech., Spinosad tech. and Emamectin benzoate tech., were added and homogenized to get a uniform slurry.
Step 4: Then half of the quantity of defoamer was added to the slurry and then the slurry was subjected to three cycles of grinding in a bead mill. Remaining half quantity of defoamer was added after the grinding process.
Step 5: Finally, thickener solution was added to obtain the title formulation.
Step 6: Sending the sample to the quality analysis;
Step 7: Packing the formulated material in suitable packaging.

Table 7: Formula I 1.5%+Formula II 24%+Pyroxasulfone 7% SC (Suspension Concentrate)
Ingredients Function Percent (w/w)
Formula I technical (94% purity) Active Ingredient 1.60
Formula II technical (95% purity) Active Ingredient 25.26
Pyroxasulfone technical (95% purity) Active Ingredient 7.37
Acrylic graft copolymer (2-Propenoic acid, 2-methyl-, polymer with .alpha.-methyl-.omega.-hydroxypoly(oxy-1,2-ethanediyl) and methyl 2-methyl-2-propenoate, graft ) Dispersing agent 1.50
Tristyryphenole with 16 moles EO Dispersing agent 2.00
Copolymer butanol EO/PO (Polyethylene-polypropylene glycol monobutyl ether) Wetting agent 3.50
Attapulgite clay Suspending agent 2.00
Polydimethyl siloxane Antifoaming agent 0.30
1,2- benzisothiazoline-3-one Preservative 0.20
1,2-Propylene glycol Antifreezing agent 5.00
Xanthan gum Thickener 0.20
Water Diluent Water 51.07
Total 100.00

Preparation of 100 kg composition of Formula I 1.5%+Formula II 24%+Pyroxasulfone 7% SC
Step 1: Preparation of gum solution: Dissolve 2 kg of 1,2-benzisothiazolin-3(2H)-one into 96 kg of Demineralized (DM) water. Now add 2 kg of xanthan gum slowly and stir till completely dissolved to form a solution. This gum solution was made 12 to 18 hours prior to use.
Step 2: Take 41.07 kg of DM water and 5 kg of 1,2-Propylene glycol into designated vessel and mix thoroughly. Add 1.5 kg of acrylic graft copolymer, 2 kg of Tristyrylphenole with 16 moles EO and 3.5 kg of Copolymer butanol EO/PO (Polyethylene-polypropylene glycol monobutyl ether), into the vessel having water and homogenize the contents for 45 to 60 minutes using high shear homogenizer.
Step 3: Then 1.60 kg of Formula I technical, 25.26 kg of Formula II technical and 7.37 kg of pyroxasulfone technical and 2 kg of attapulgite clay were added and homogenized to get a uniform slurry for grinding.
Step 4: Then half of the quantity of polydimethyl siloxane was added to the slurry and then the slurry was subjected to three cycles of grinding in a bead mill till desired particle size achieved. Remaining half quantity of polydimethyl siloxane was added after the grinding process.
Step 5: Finally, 10 kg of remaining gum solution added and homogenize it to obtain the title formulation.
Step 6: Sending the sample to the quality analysis;
Step 7: Packing the formulated material in suitable packaging.

Storage stability study of Formula I 1.5%+Formula II 24%+Pyroxasulfone 7% SC (Suspension Concentrate):
The composition of Formula I 1.5%+Formula II 24%+Pyroxasulfone 7% SC 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 three months, at 40°C, designated as T2.

Table 8: Storage stability of Formula I 1.5%+Formula II 24%+Pyroxasulfone 7% SC (Suspension Concentrate):
Parameters T0 T1 (AHS),for 14 days at 54 'C. T2- for three months at 40 'C
Formula I content (%) (-5% to +10% range) 1.72 1.71 1.70
Formula II content (%), (-5% to +5% range) 26.30 26.28 26.28
Pyroxasulfone content (%) (-5% to +10% range) 7.95 7.94 7.94
suspensibility (minimum 80%) 98.00 98.20 98.00
pH range (5 to 7, 1% aq. Suspension) 6.50 6.40 6.40
pourability (95% minimum) 98.50 98.20 98.00
Viscosity at spindle no. 62, 20 rpm (350 to 800 cps) 640 650 660

The SC formulation of Formula I 1.5%+Formula II 24%+Pyroxasulfone 7% meets all the required parameters like actives ingredients content, suspensibility of composition, pH range, pourability and viscosity were maintained at AHS conditions (T1) and at condition of 40’C for 3 months (T2).

Example 6
Preparation of composition of Formula I, Formula II and Pendimethalin into Emulsifiable Concentrate (EC) form:
Weighing the raw materials according to the batch size as follows:
Solvent, emulsifier and technical.
Charge the solvents and emulsifiers into a vessel and then add required quantity of technical and mix till it gets completely homogenized.

Table 9: Formula I 0.8% + Formula II 13% + Pendimethalin 24% EC
Ingredients Function Percent (w/w)
Formula I technical (94% purity) Active Ingredient 0.85
Formula II technical (95% purity) Active Ingredient 13.68
Pendimethalin technical (90% purity) Active Ingredient 26.67
Polyoxyethylene sorbitan monooleate Emulsifier 12.50
Tristyrylphenol Ethoxylate Phosphate Ester Emulsifier 7.50
N-Methyl-2-pyrrolidone Solvent 10.00
Aromatic solvent (solvent naphtha) Solvent 28.80
Total 100.00

Preparation of 100 kg composition of Formula I 0.8% + Formula II 13% + Pendimethalin 24% EC
Weighing the raw materials according to the batch size as follows:
Add 28.80 kg of aromatic solvent (solvent naphtha), 10 kg of N-Methyl-2-pyrrolidone into the vessel. Slowly add 12.5 kg of polyoxyethylene sorbitan monooleate and 7.5 kg of tristyrylphenol ethoxylate phosphate ester with slow stirring.
Add 0.85 kg of Formula I technical, 13.68 kg of Formula II technical and 26.67 kg of pendimethalin technical and mix it properly for 30 to 45 minutes. Collect the sample for quality check and pack it in suitable container.

Storage stability study of Formula I 0.8%+Formula II 13%+Pendimethalin 24% EC (Emulsifiable concentrate)
The composition of Formula I 0.8%+Formula II 13%+Pendimethalin 24% EC 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 three months, at 40°C, designated as T2.

Table 10: Storage stability of Formula I 0.8% + Formula II 13% + Pendimethalin 24% EC (Emulsifiable concentrate)
Parameters with specifications T0 T1 (AHS),for 14 days at 54 'C. T2- for three months at 40 'C
Formula I content (%) (-5% to +10% range) 0.91 0.90 0.90
Formula II content (%), (-5% to +5% range) 14.22 14.21 14.20
Pendimethalin content (%) (-5% to +5% range) 27.85 27.83 27.82
Emulsion stability (2 ml formulation in 98 ml 342 ppm hard water), maximum 2 ml creaming or sediment after 1 hour 0 ml 0.2 ml 0.2 ml
pH (5% in DM water, 5.5 to 7.5) 6.3 6.3 6.2
Cold test (at 10 ºC temperature) Any separation or creaming max. 2 ml after 1 hour pass pass pass
Flash point (above 24.5 0C) complies complies complies

The storage stability parameters of actives ingredients content, emulsion stability, pH range, cold test and flash point were maintained at AHS conditions (T1) and at condition of 40’C for 3 months (T2).

Example 7
Preparation of composition of Formula I, Formula II and Pendimethalin into Zeon Concentrate (ZC) form:
Table 11: Formula I 1.2%+Formula II 10%+Pendimethalin 24% ZC
Ingredients Function Percent (w/w)
Formula I technical (94% purity) Active Ingredient 1.28
Formula II technical (95% purity) Active Ingredient 10.53
Pendimethalin technical (90% purity) Active Ingredient 26.67
Alkyl phenyl polyglycol ether Dispersing agent 2.50
Alkyl naphthalene sulfonate condensate Dispersing agent 0.50
Sodium Isopropyl Naphthalene Sulfonate Wetting agent 2.00
Polymethylene polyphenylene isocyanate Wall forming material 0.50
Diethylenetriamine Wall forming material 0.25
Magnesium sulfate heptahydrate Antifreezing agent 2.50
Tributyl phenyl polyglycol ether Suspending agent 1.50
Polydimethylsiloxane Antifoaming agent 0.30
Hydrochloric acid Buffering agent 0.50
1,2-benzisothiazolin-3(2H)-one Preservative 0.20
Mono ethylene glycol Antifreezing agent 2.50
Xanthan gum Thickener 0.15
Water Solvent/diluent 48.13
Total 100.00

Preparation of 100 kg composition of Formula I 1.2%+Formula II 10%+Pendimethalin 24% ZC
Weighing the raw materials according to the batch size as follows:
Part A: Preparation of gum solution:
Dissolve 2 kg of 1,2-benzisothiazolin-3(2H)-one into 96 kg of Demineralized (DM) water. Now add 1.5 kg of xanthan gum slowly and stir till completely dissolved to form a solution. This gum solution was made 12 to 18 hours prior to use.
Part B: Preparation of CS (Capsule Suspension) formulation:
Step 1: Aqueous Phase: Charge DM water (20 kg) to a stainless-steel vessel equipped with a high-speed stirrer. Under agitation, add Sodium Isopropyl Naphthalene Sulfonate (2.00 kg), magnesium sulphate heptahydrate (2.5 kg) and Alkyl naphthalene sulfonate condensate (0.50 kg) into the vessel. Now add 50% quantity of antifoam to avoid foam generation in this vessel.
Step 2: Organic Phase: Charge Pendimethalin technical (26.67 kg) into second stainless-steel reactor and melt it. Afterwards, charge Polymethylene polyphenylene isocyanate (0.50 kg) to the reactor. Mix well.
Step 3: Start the high shear disperser of aqueous phase and charge the ‘Organic Solution’ into the ‘Aqueous Phase Solution’ under gravity in specific rate so that required particle size can be achieved and continue to shear for 30 min. Then, start heating the reactor to around 50 °C and stir the formulation under slow rpm for 3 to 4 hours so that polymerization reaction gets completed.
Step 4: Now add Diethylenetriamine (0.25 kg) so that residual wall forming material 1 can be consumed and stir for 1 more hour at the same temperature and if required add half quantity of antifoam to remove foam generating due to CO2 during reaction.
Step 5: After the wall polymerization reaction, increase the agitator to high speed. Add the rest half quantity of antifoam to the formulation. Under slight vacuum, allow the mixture to de-gas for approximately 30 minutes to remove CO2 from the solution. Add the Xanthan gum solution (3.75 kg) and mix for some minutes. Add hydrochloric acid (0.50 kg) for pH adjustment. Check the formulation to specifications.
Part C: Preparation of SC (Suspension Concentrate) formulation
Step 1: Charge the required quantity of (20.63 kg) water to a vessel, equipped with bulk agitator and a high shear homogenizer and start agitation. Add Mono ethylene glycol (2.50 kg), Alkyl phenyl polyglycol ether (2.5 kg) and mix until uniform. Add the antifoaming agent and ensure that it is well dispersed. Add Tributyl phenyl polyglycol ether (1.50 kg) and mix until uniform.
Step 2: Now add the Formula II technical (10.53 kg) and Formula I technical (1.28 kg) and continue agitating the vessel contents until all components get homogenized. Mill this pre-mix through a Colloid mill and subsequently through a Dyno mill to meet the specified particle size.
Step 3: Add remaining antifoaming agent to this SC mill base to a vessel, equipped with bulk agitator. Mix until uniform. Add the required amount of 2% aqueous pre-gel and continue agitation until the formulation is homogeneous and has the target viscosity. Mix well.
Part D: Preparation of ZC Formulation
Step 1: Charge the required quantity of SC formulation into a vessel, equipped with bulk agitator and start agitation. Add the CS Premix to this slurry and mix slowly until uniform. Add the required amount of gum solution (3.75 kg) and continue agitation until the formulation is homogeneous and a target viscosity of around 600-800 m cPs is reached. Mix well.
Step 2: Final product is sent for QC approval.
Step 3: After approval, material is packed in required pack sizes.
Example 8
Preparation of composition of Formula I, Formula II and Pyroxasulfone in Wettable Powder (WP) form.
Step 1: weighing the raw materials according to the batch size as follows:
Fillers, dispersing agent, wetting agent, Formula I technical, Formula II technical and pyroxasulfone technical, anticaking agent, carrier.
Weigh all these row materials in a pre-blender and mix it for 1 hr.
Step 2: Milling the sample through air jet mill instrument at inlet pressure 2-3 kg/cm2, grinding pressure 6 kg/ cm2 and checking for the particle size D90< 10 micron.
Step 3: Collecting the milled material and post blending the sample for 1 hr.;
Step 4: Sending the sample to the quality analysis;
Step 5:Packing the formulated material in suitable packaging.

Table 12: Formula I 2%+Formula II 32.5%+Pyroxasulfone 12% WP (Wettable Powder)
Ingredients Function Percent (w/w)
Formula I technical (94% purity) Active Ingredient 2.13
Formula II technical (95% purity) Active Ingredient 34.21
Pyroxasulfone technical (95% purity) Active Ingredient 12.63
Phenol sulfonic acid-formaldehyde Dispersing agent 2.50
Sodium Poly alkyl naphthalene sulphonate Dispersing agent 2.50
Alkyl naphthalene sulfonate (ANS)
condensate blend Wetting agent 4.00
Silicone dioxide Anti-caking agent 1.50
China clay Carrier 40.53
Total 100.00

Preparation of 100 kg composition of Formula I 2%+Formula II 32.5%+Pyroxasulfone 12% WP
Step 1-Charge 2.13 kg of Formula I technical, 34.21 kg of Formula II technical, 12.63 kg of pyroxasulfone technical, 40.53 kg of China clay, 1.50 kg of silicone dioxide, 4 kg of alkyl naphthalene sulfonate (ANS), 2.50 kg of sodium poly alkyl naphthalene sulphonate, 2.50 kg of phenol sulfonic acid-formaldehyde in premixing blender for homogenization for 1 hour.
Step 2- The mixture was milled through air jet mill instrument (Inlet pressure 2-3 kg/cm2, grinding pressure 6 kg/ cm2) to obtain the desired particle size (D90 < 10 microns).
Step 3- Collecting the milled material and post blending the material for 1 hour followed by packing the material in a suitable package.

The composition of Formula I 2%+Formula II 32.5%+Pyroxasulfone 12% WP 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. The composition meets all the required parameters for stability.

Example 9

Biological examples:

Evaluation of synergistic effect of present compositions.
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).

Trial 1: Weed control and phytotoxicity in soybean crop.
Crop: Soybean
Plot size: 8m x 5m.
Application Time: Pre emergence (2 days after sowing), before crop and weed emergence.
Spray volume: 500 Liters per hectare.
Spray equipment: Battery powered knap sack sprayer.
Observations:
Observations were recorded on weed density, plant growth parameter and grain yield. A quadrate of 0.25 m2 (50cm x 50cm) was randomly selected at four spots per plot. Species wise weed count was recorded on 15, 30 and 45 DAS (days after sowing) and weed density was expressed as number/m2. Weed control was calculated by given formula.

Pod count: count the number of mature pods per plant, 20 plants per plot before harvest.
Grain yield: Record the observations on grain/seed yield per plot and convert into kg per hectare.
Table 13: Treatments
S.No. Treatments Dose per hectare
active ingredients (gram) formulations (gram or ml)
T1 Control - -
T2 Formula I 84% WG 30 35.71 g
T3 Formula I 84% WG 25 29.76 g
T4 Formula I 84% WG 10 11.90 g
T5 Formula II 39.6% SC (48% w/v) 250 521 ml
T6 Formula II 39.6% SC (48% w/v) 300 625 ml
T7 Formula II 39.6% SC (48% w/v) 350 729 ml
T8 Pyroxasulfone 85% WG 100 118 g
T9 Pyroxasulfone 85% WG 125 147 g
T10 Pyroxasulfone 85% WG 150 176 g
T11 Formula I 84% WG+Formula II 48% SC 30+250 35.71 g + 521 ml
T12 Formula I 84% WG+Formula II 48% SC 25+300 29.76 g + 625 ml
T13 Formula I 84% WG+Formula II 48% SC 10+350 11.90 g + 729 ml
T14 Formula I 15%+Pyroxasulfone 50% WG 30+100 200 g
T15 Formula I 10%+Pyroxasulfone 50% WG 25+125 250 g
T16 Formula I 5%+Pyroxasulfone 75% WG 10+150 200 g
T17 Formula II 48% SC+Pyroxasulfone 85% WG 250+100 521 ml + 118 g
T18 Formula II 48% SC+Pyroxasulfone 85% WG 300+125 625 ml + 147 g
T19 Formula II 48% SC+Pyroxasulfone 85% WG 350+150 729 ml + 176 g
T20 Formula I 5%+Chlorimuron ethyl 1.5%+Pyroxasulfone 30% WDG 20+6+120 400 g
T21 Formula I 3%+Formula II 25%+Pyroxasulfone 10% WG 30+250+100 1000 g
T22 Formula I 2.5%+Formula II 30%+Pyroxasulfone 12.5% WG 25+300+125 1000 g
T23 Formula I 1.25%+Formula II 43.75%+Pyroxasulfone 18.75% WG 10+350+150 800 g
T21 to T23-present composition; T11 to T19-known binary mixtures/tank mixes; T20-known ternary combination, T2 to T10-market products; WG-wettable granules, SC-suspension concentrate.

Weed density in control plot (Number / 0.25 m2 quadrant)
Weed species 15 DAS 30 DAS 45 DAS
Monocot weed Echinochloa colona 12.83 18.63 19.25
Digitaria sanguinalis 9.52 10.37 10.52
Dicot weed Commelina benghalensis 10.96 26.82 28.64
Euphorbia geniculata 4.83 6.34 6.95
Parthenium hysterophorus 2.85 4.26 4.53
Sedges weed Cyperus rotundus 3.16 6.48 6.93

Table 14a: Weed control in soybean.
S.No. Weed control (%)
at 15 days at 30 days
observed expected as per Colby formula ratio Synergism (Y/N) observed expected as per Colby formula ratio Synergism (Y/N)
T1 - - - - - - - -
T2 60.5 - - - 47.2 - - -
T3 54.3 - - - 40.4 - - -
T4 31.3 - - - 13.8 - - -
T5 48.3 - - - 32.5 - - -
T6 60.2 - - - 44.9 - - -
T7 66.8 - - - 52.8 - - -
T8 30.8 - - - 14.6 - - -
T9 44.3 - - - 30.2 - - -
T10 53.7 - - - 36.5 - - -
T11 80.2 79.58 1.01 Y 62.7 64.36 0.97 N
T12 83.4 81.81 1.02 Y 67.0 67.16 1.00 N
T13 78.1 77.19 1.01 Y 57.6 59.31 0.97 N
T14 73.3 72.67 1.01 Y 52.3 54.91 0.95 N
T15 75.8 74.55 1.02 Y 58.2 58.40 1.00 N
T16 69.2 68.19 1.01 Y 43.2 45.26 0.95 N
T17 64.8 64.22 1.01 Y 40.8 42.36 0.96 N
T18 79.2 77.83 1.02 Y 61.6 61.54 1.00 N
T19 85.7 84.63 1.01 Y 68.5 70.03 0.98 N
T20 91.6 - - - 87.7 - - -
T21 100.0 85.87 1.16 Y 99.5 69.56 1.43 Y
T22 100.0 89.87 1.11 Y 100.0 77.08 1.30 Y
T23 100.0 89.44 1.12 Y 100.0 74.16 1.35 Y

Table 14b: Weed control in soybean.
S.No. Weed control (%)
at 45 days
observed expected as per Colby formula ratio Conclusion
T1 - - - -
T2 31.2 - - -
T3 25.6 - - -
T4 1.8 - - -
T5 17.3 - - -
T6 28.6 - - -
T7 37.5 - - -
T8 1.5 - - -
T9 14.2 - - -
T10 21.7 - - -
T11 40.2 43.10 0.93 N
T12 44.7 46.88 0.95 N
T13 35.7 38.63 0.92 N
T14 28.6 32.23 0.89 N
T15 35.2 36.16 0.97 N
T16 20.5 23.11 0.89 N
T17 15.8 18.54 0.85 N
T18 36.8 38.74 0.95 N
T19 46.3 51.06 0.91 N
T20 77.3 - - -
T21 98.3 43.96 2.24 Y
T22 100.0 54.42 1.84 Y
T23 99.2 51.94 1.91 Y

The field trial data collected and analysed (Table 2a and Table 2b). It was inferred that present ternary composition (Formula I+Formula II+pyroxasulfone) at various doses (T21 to T23) has synergistic effects on mixed weed flora (grasses, broad leaf and sedges weed) and provides effective control (>98%) up to 45 days after sowing. All known binary mixtures and tank mixes (T11 to T19) provide synergistic control up to 15 days only, as fresh germination of weeds observed after that, so failed to provide residual weed control. All the present ternary composition (T21 to T23) provides higher degree of weed control (i.e. 100% at 15 DAS, >99% at 30 DAS and >98% at 45 DAS) as compared to known ternary combinations (T20), i.e. 91.6% at 15 DAS, 87.7% at 30 DAS and 77.3% at 45 DAS.

Table 15: Effect of synergistic composition on plant growth and yield.
S.No. average number of pods per plant increase in pods/plant over T1 seed yield (kg/h) increase in seed yield over T1
T1 24.73 0.0 1206 0.0
T2 30.47 23.2 1756 45.6
T3 30.37 22.8 1737 44.0
T4 26.58 7.5 1686 39.8
T5 31.76 28.4 1740 44.3
T6 32.35 30.8 1757 45.7
T7 31.88 28.9 1745 44.7
T8 29.11 17.7 1525 26.5
T9 29.53 19.4 1586 31.5
T10 30.48 23.3 1598 32.5
T11 37.34 51.0 2280 89.1
T12 37.96 53.5 2388 98.0
T13 36.32 46.9 2314 91.9
T14 32.58 31.7 2337 93.8
T15 36.21 46.4 2350 94.9
T16 30.46 23.2 2324 92.7
T17 29.78 20.4 2357 95.4
T18 36.88 49.1 2377 97.1
T19 38.56 55.9 2368 96.4
T20 39.93 61.5 2534 110.1
T21 45.13 82.5 2845 135.9
T22 45.27 83.1 2857 136.9
T23 44.97 81.8 2843 135.7

The soybean plots treated with present ternary composition (T21 to T23) bear higher number of pods (minimum 44.97 pods/plant) and produces higher (<25%) seed yield as compared to known ternary combinations (T20).
The visual observations on phytotoxicity show present composition (T21 to T23) found safe to the soybean crop and does not have adverse effect on plant growth, pod bearing capacity and on seed yield.

Trial 2: Weed control in soybean crop.
Crop: Soybean
Plot size: 10m x 5m.
Application Time: Pre emergence (1 days after sowing), before crop and weed emergence.
Spray volume: 500 litres per hectare.
Spray equipment: Battery powered knap sack sprayer.
Observations: as per experiment 1.
Weed flora of trial plot comprises of grassy weeds (52%)-Echinochloa colona, Eleusine indica;
Broad leaf weeds (42%)-Commelina benghalensis, Commelina communis, Acalypha indica, Digera arvensis; Sedge weed (6%)-Cyperus rotundus.

Table 16: Treatments.
S.No. Treatments Dose/hectare (active ingredients in gram)
T1 Control -
T2 Formula I 84% WG 22.5
T3 Formula I 84% WG 30
T4 Formula II 48% SC 300
T5 Formula II 48% SC 250
T6 Pendimethalin 30% EC 750
T7 Pendimethalin 30% EC 600
T8 Formula I 84% WG +Formula II 48% SC 22.5+300
T9 Formula I 84% WG +Formula II 48% SC 30+250
T10 Formula I 0.9%+Pendimethalin 30% SE 22.5+750
T11 Formula I 1.2%+Pendimethalin 24% SE 30+600
T12 Formula II 12%+Pendimethalin 30% SE 300+750
T13 Formula II 10%+Pendimethalin 24% EC 250+600
T14 Formula II 9.29%+oxyfluorfen 1.57%+pendimethalin 28.57% SE 300+51+928
T15 Formula I 0.75%+Formula II 10%+Pendimethalin 25% SE 22.5+300+750
T16 Formula I 1.2%+Formula II 10%+Pendimethalin 24% ZC 30+250+600
T15 & T16-present compositions; T14-priot art combination; T8 & T9-binary tank mixes; T10 to T3-known binary ready mixes; T2 to T7-market products; SE-suspo emulsion, ZC-Zeon concentrate.

Table 17a: Weed control in soybean.
S.No. Weed control (%)
at 15 days at 30 days
observed expected as per Colby formula ratio Synergism (Y/N) observed expected as per Colby formula ratio Synergism (Y/N)
T1 - - - - - - - -
T2 51.7 - - - 40.2 - - -
T3 61.4 - - - 50.7 - - -
T4 62.3 - - - 55.6 - - -
T5 49.6 - - - 40.1 - - -
T6 60.7 - - - 50.2 - - -
T7 56.3 - - - 42.5 - - -
T8 82.2 81.79 1.01 Y 70.4 73.45 0.96 N
T9 81.4 80.55 1.01 Y 67.8 70.47 0.96 N
T10 82.4 81.02 1.02 Y 66.3 70.22 0.94 N
T11 85.8 83.13 1.03 Y 67.8 71.65 0.95 N
T12 87.3 85.18 1.02 Y 76.4 77.89 0.98 N
T13 80.2 77.98 1.03 Y 64.2 65.56 0.98 N
T14 97.8 - - - 91.6 - - -
T15 100.0 92.84 1.08 Y 100.0 86.78 1.15 Y
T16 100.0 91.50 1.09 Y 99.7 83.02 1.20 Y

Table 17b: Weed control in soybean.
S.No. Weed control (%)
at 45 days
observed expected as per Colby formula ratio Synergism (Y/N)
T1 - - - -
T2 20.6 - - -
T3 32.5 - - -
T4 38.2 - - -
T5 23.0 - - -
T6 32.8 - - -
T7 22.4 - - -
T8 45.7 50.93 0.90 N
T9 41.3 48.03 0.86 N
T10 42.8 46.64 0.92 N
T11 43.5 47.62 0.91 N
T12 54.6 58.47 0.93 N
T13 35.3 40.25 0.88 N
T14 85.2 - - -
T15 98.3 67.03 1.47 Y
T16 95.2 59.67 1.60 Y

The field trial results show both the treatment of present composition (T15 & T16) provides synergistic and residual control (up to 45 DAS) of mixed weed flora in soybean crop. All known binary tank mixes (T8 & T9), binary ready mixes (T10 to T13) and ternary ready mix (T14) provides effective control of mixed weed flora up to 15 days only. Both the present compositions (T15 & T16) found safe to the soybean crop.

Trial 3: Weed control in sugarcane crop.
Crop: Sugarcane
Plot size: 8m x 6m.
Application Time: Pre emergence (3 days after sowing), before crop and weed emergence.
Spray volume: 500 Liters per hectare.
Spray equipment: Battery powered knap sack sprayer.
Observations: as per experiment 1.
Weed flora of trial plot comprises of grassy weeds (48%)-Brachiaria spp., Sorghum halepense, Echinochloa colona, Eleusine indica; Broad leaf weeds (34%)-Trianthema monogyna, Amaranthus spp., Convolvulus spp, ; Sedge weed (18%)-Cyperus rotundus, Cyperus esculentus.

Table 18: Weed control in sugarcane crop.
Treatments Dose/hectare (active ingredients in gram) Weed control (%) at
45 days 60 days
T1- Control - - -
T2- Formula I 84% WG 30 40.18 24.26
T3- Formula II 48% SC 480 61.72 40.65
T4- Pyroxasulfone 85% WG 140 40.58 26.32
T5- Formula I 1.5%+Formula II 24%+Pyroxasulfone 7% SC 30+480+140 98.68 94.78
T6- Chlorimuron ethyl 0.3%+Formula II 20%+Pyroxasulfone 4% WG 7.5+500+100 85.35 73.73
T7- Metribuzin 20%+Formula II 20%+Pyroxasulfone 4.8% WG 500+500+120 89.92 79.62
T5-present composition; T6 & T7-prior art combinations; SC-suspension concentrate.

The pre-emergent application of present compositions (T5) provides synergistic and residual control of mixed weed flora in sugarcane crop on 45 and 60 days. The present composition provides >98% and >94% weed control on 45 and 60 days respectively, whereas known ternary ready-mix formulations T6 provide 85.35% and 73.73% weed control on 45 and 60 days respectively; T7 provides 89.92% and 79.62% weed control on 45 and 60 days respectively. The present composition (T5) does not show any kind of phytotoxicity symptoms on sugarcane crops.

Trial 4: Weed control in soybean crop.
Crop: Soybean
Plot size: 8m x 6m.
Application Time: Pre emergence (2 days after sowing), before crop and weed emergence.
Spray volume: 500 litres per hectare.
Spray equipment: Battery powered knap sack sprayer.
Observations: as per experiment 1.
Table 19: Weed control in soybean.
Treatments Dose/hectare (active ingredients in gram) Weed control (%) at 30 Days
Observed Expected as per Colbys formula
T1-Control - - -
T2-Formula I 84% WG 20 36.96 -
T3-Formula II 48% SC 325 48.47 -
T4-Pyroxasulfone 85% WG 120 33.16 -
T5-Pendimethalin 30% EC 600 44.78 -
T6-Formula I 2%+Formula II 32.5%+Pyroxasulfone 12% WP 20+325+120 98.85 78.29
T7-Formula I 0.8%+Formula II 13%+Pendimethalin 24% EC 20+325+600 98.62 82.06
T6 & T7-present compositions, WP-wettable powder, EC-emulsifiable concentrate.
Both the present compositions (T6 & T7) provide synergistic control of mixed weed flora in soybean crop.
, C , Claims:I/We Claim,
1. A synergistic ternary herbicidal composition comprising:
a. Compound (A) Formula I (N-(2,6-dichlorophenyl)-5-ethoxy-7-fluoro-[1,2,4] triazolo[1,5-c]pyrimidine-2- sulfonamide);
b. Compound (B) Formula II (N-{2,4-Dichloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]phenyl}methanesulfonamide);
c. Compound (C) selected from Pyroxasulfone or Pendimethalin; and
d. One or more inactive excipients.

2. The synergistic ternary herbicidal composition as claimed in claim 1, wherein Compound (A) Formula I is in amount of 2.0% to 10.0% w/w; compound (B) Formula II is in amount of 5.0% to 50.0% w/w; and compound (C) is selected from Pyroxasulfone or Pendimethalin is in amount of 5% to 30.0% w/w.

3. The synergistic ternary herbicidal composition as claimed in claim 1, wherein one or more inactive excipients is selected from the group comprising of wetting agent, dispersing agent, disintegrating agent, emulsifier, defoamer, anti-freezing agent, preservative, filler, thickener/suspending agent, pH stabilizer, anticaking agent, filler, solvent or a combination thereof and other additives, if required in a formulation.

4. The synergistic ternary herbicidal composition as claimed in claim 1, wherein the formulation for the said composition is selected from Water dispersible granules (WDG/WG), Water soluble granules (SG), Emulsifiable granule (EG), Wettable powder (WP), Soluble powder (SP), Emulsifiable powder (EP), Oil dispersible powder (OP), Soluble Tablet (ST), Capsule suspension/Micro capsule (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion water-in-oil (EO), Emulsion oil-in-water (EW), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Suspo Emulsion (SE), Soluble Liquid/Concentrate (SL), mixed formulation of CS and SC (ZC), mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

5. The synergistic ternary herbicidal composition as claimed in claim 4, wherein the Wettable Granules (WDG/WG) formulation comprises:
i. Compound (A) Formula I present in an amount of 0.2% to 10.0% w/w;
ii. Compound (B) Formula II present in an amount of 5.0% to 50.0% w/w;
iii. Compound (C) is selected from Pyroxasulfone or Pendimethalin present in an amount of 5% to 30.0% w/w;
iv. Wetting agent in an amount of 1.0% to 5.0 % w/w;
v. Dispersing agent in an amount of 2.0% to 20.0% w/w;
vi. Disintegrating agent in an amount of 1.0% to 20.0% w/w;
vii. Antifoaming agent in an amount of 0.1% to 5.0% w/w;
viii. Binding agent in an amount of 1.0% to 10% w/w; and
ix. Carrier & filler are in amount of quantity sufficient.

6. The synergistic ternary herbicidal composition as claimed in claim 4, wherein the Suspo Emulsion (SE) formulation comprises:
i. Compound (A) Formula I present in an amount of 0.2% to 10.0% w/w;
ii. Compound (B) Formula II present in an amount of 5.0% to 50.0% w/w;
iii. Compound (C) is selected from Pyroxasulfone or Pendimethalin present in an amount of 5% to 30.0% w/w;
iv. Wetting agent in an amount of 1.0% to 5.0 % w/w;
v. Dispersing agent in an amount of 2.0% to 10.0% w/w;
vi. Solvent and Co-solvent in an amount of 5.0% to 40.0% w/w;
vii. Emulsifier in an amount of 2.0% to 20.0% w/w;
viii. Suspending agent in an amount of 0.2% to 5.0% w/w;
ix. Anti-freezing agent in an amount of 0.1% to 5.0% w/w;
x. Antifoaming agent in an amount of 0.1% to 5.0% w/w;
xi. Preservatives in an amount of 0.1% to 2.0% w/w;
xii. Thickener in an amount of 0.1% to 1.0% w/w; and
xiii. Diluent is in amount quantity sufficient.

7. The synergistic ternary herbicidal composition as claimed in claim 4, wherein the Suspension Concentrate (SC) formulation comprises:
a. Compound (A) Formula I present in an amount of 0.2% to 10.0% w/w;
b. Compound (B) Formula II present in an amount of 5.0% to 50.0% w/w;
c. Compound (C) is selected from Pyroxasulfone or Pendimethalin present in an amount of 5% to 30.0% w/w;
d. Wetting agent in an amount of 1.0% to 5.0 % w/w;
e. Dispersing agent in an amount of 2.0% to 10.0% w/w;
f. Suspending agent in an amount of 0.2% to 5.0% w/w;
g. Anti-freezing 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. Preservatives in an amount of 0.1% to 2.0% w/w;
j. Thickener in an amount of 0.01% to 5.0% w/w; and
k. Distilled Mineral water is in quantity sufficient amount.

8. The synergistic ternary herbicidal composition as claimed in claim 4, wherein the Emulsifiable Concentrate (EC) formulation comprises:
a. Compound (A) Formula I present in an amount of 0.2% to 10.0% w/w;
b. Compound (B) Formula II present in an amount of 5.0% to 50.0% w/w;
c. Compound (C) is selected from Pyroxasulfone or Pendimethalin present in an amount of 5% to 30.0% w/w;
d. Emulsifier present in an amount of 1.0% to 40.0 % w/w;
e. Solvent is in quantity sufficient amount.

9. The synergistic ternary herbicidal composition as claimed in claim 4, wherein the Zeon Concentrate (ZC) formulation comprises:
a. Compound (A) Formula I present in an amount of 0.2% to 10.0% w/w;
b. Compound (B) Formula II present in an amount of 5.0% to 50.0% w/w;
c. Compound (C) herbicide is selected from Pyroxasulfone or Pendimethalin present in an amount of 5% to 30.0% w/w;
d. Wetting agent in an amount of 1.0% to 5.0 % w/w;
e. Dispersing agent in an amount of 2.0% to 10.0% w/w;
f. Wall forming material in an amount of 0.5% to 5% w/w;
g. Suspending agent in an amount of 0.2% to 5.0% w/w;
h. Anti-freezing agent in an amount of 0.1% to 5.0% w/w;
i. Antifoaming agent in an amount of 0.1% to 5.0% w/w;
j. Preservatives in an amount of 0.1% to 2.0% w/w;
k. Thickener in an amount of 0.01% to 5.0% w/w; and
l. Diluent is in quantity sufficient amount.

10. The synergistic ternary herbicidal composition as claimed in claim 4, wherein the Wettable Powder (WP) formulation comprises:
x. Compound (A) Formula I present in an amount of 0.2% to 10.0% w/w;
xi. Compound (B) Formula II present in an amount of 5.0% to 50.0% w/w;
xii. Compound (C) is selected from Pyroxasulfone or Pendimethalin present in an amount of 5% to 30.0% w/w;
xiii. Wetting agent in an amount of 1.0% to 10.0 % w/w;
xiv. Anti-caking agent in an amount of 0.1% to 5.0% w/w;
xv. Carrier & filler are in amount of quantity sufficient.

11. The synergistic ternary herbicidal composition as claimed in claims 5, 6, 7, 8, 9, and 10, 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, dialkyl naphthalene sulphate sodium salt, dioctyl succinate, sodium lauryl sulphate, 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 Trisiloxane, polyalkyleneoxide modified polydimethylsiloxane, may be liquid or powder form or a combination thereof.

12. The synergistic ternary herbicidal composition as claimed in claims 5, 6, 7, 8, 9 and 10, wherein Dispersing agent is selected from the group comprising acrylic graft copolymer, 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), poly acrylate copolymer, Potassium laurate, polyarylphenyl ether phosphate, Tri styryl phenol ethoxylate, ethoxylated tristyryl phenol sulphate, acrylic polymer amine salt, naphthalene sulfonic acid-sodium salt condensate with formaldehyde, alkylated naphthalene sulfonate-sodium salt, ethoxylated oleylcetyl alcohol, polyalkelene glycol ether, ethoxylated fatty alcohol, alkyl sulfonate, styrene acrylic copolymer, alkyl phenol polyglycol ether, modified 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.

13. The synergistic ternary herbicidal composition as claimed in claim 6, 7, 8 and 9, wherein solvent and cosolvent 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, mineral oil, methylated seed oil-methyl ester of palm oil/soybean oil/castor oil/cotton seed oil/blend of two or more seed oil.

14. The synergistic ternary herbicidal composition as claimed in claims 5, 6, 7, 8, 9 and 10, 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.

15. The synergistic ternary herbicidal composition as claimed in claims 6, 7, 8 and 9, wherein Anti freezing agent is selected from ethylene glycol, propane diols, glycerin or the urea, glycol, propylene glycol, monoethylene glycol, diethylene glycol, polypropylene glycol, polyethylene glycol, glycerin, urea, magnesium sulfate heptahydrate, sodium chloride or a combination thereof.

16. The synergistic ternary herbicidal composition as claimed in claims 6, 7, 8 and 9, wherein Preservative is selected from benzisothiazolin-3-one, formaldehyde, sodium benzoate, sodium o-phenyl phenate, potassium sorbate, copper pyrithione, zinc pyrithione, 1,2-benzisothiazolin-3(2H)-one, 2-bromo-2-nitropropane-1,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one or a combination thereof.

17. The synergistic ternary herbicidal composition as claimed in claim 6, 8 and 9, 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.

18. The synergistic ternary herbicidal composition as claimed in claim 5 and 10, wherein Carriet/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.
19. 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.

20. The synergistic ternary herbicidal composition as claimed in claims 6, 7, and 9, wherein Thickeners/ buffering agent/suspending 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.

21. The synergistic ternary herbicidal composition as claimed in claim 5 and 10, 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.

22. The synergistic ternary herbicidal composition as claimed in claim 5 and 10, wherein binder is selected from water-soluble 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, a natural gum, lignosulphonate, China clay, bentonite, fuller’s earth, zeolite, quartz, precipitated silica, palygorskite, sepiolite, halloysite, and a combination thereof.

23. The synergistic ternary herbicidal composition as claimed in claim 5 and 10, 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.

24. The synergistic ternary herbicidal composition as claimed in claim 9, wherein wall forming material is selected from Tetramethylene diisocyanate, Penta methylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4,4-diphenylmethene diisocyanate (MDI), polymethylene polyphenylene isocyanate, 2,4,4’-diphenyl ether tri-isocyanate, 3,3’-dimethyl-4,4’-diphenyl diisocyanate, 3,3’-dimethoxy-4,4’-diphenyl diisocyanate, 1,5-naphthylene diisocyanate and 4,4’4"-triphenylmethane tri-isocyanate, toluene diisocyanate or polymethylene polyphenylisocyanate, polyurethane comprising of polyfunctional iso cyanate and a polyamine in polarized form;, Diethylene triamine, Ammonia, hexamine, ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetra ethylene pentaamine, pentaethylenehexamine, 4,9-dioxadodecane-1, 12-diamine, 1,3- phenylenediamine, 2,4- and 2,6-toluenediamine and 4,4’-diaminodiphenylmethane, 1,3-phenylenediamine, 2,4- and 2,6-toluenediamine, 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 1,3,6-triaminonaphthalene, 2,4,4′-triaminodiphenyl ether, 3,4,5-triamino-1,2,4-triazole and 1,4,5,8-tetraminoanthraquinone or their combinations thereof.

Dated this 21st Day of February, 2025