DESC:Technical field of the Invention:
The present invention relates to a synergistic herbicidal formulation comprising; (A) Pyroxasulfone; (B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione; and (C) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam along with one or more agrochemically acceptable adjuvants/excipients, for effective removal or control of weeds and undesirable vegetation in agricultural as well as non-agricultural land. The invention also relates to process for preparation of said synergistic herbicidal formulation.

Background of the Invention:
Weeds are the most important biotic constraints to agricultural production in both developing and developed countries. Weeds compete with crops for sunlight, water, nutrients, and space. In addition, they harbor insects and pathogens, which attack crop plants. Furthermore, they destroy native habitats, threatening native plants and animals. In general, weeds are majorly responsible for highest potential yield loss to crops. Yield losses in crops due to weeds depend on several factors such as weed emergence time, weed density, type of weeds, and crops, etc. Most of the times, the uncontrolled weeds can result in 100% yield loss.

In developing countries, where farm size is small, weeds are removed manually. This practice is becoming less common as a result of the urbanization. Hand weeding is being replaced by herbicide use. In developed countries, herbicides are already widely used to control weeds. However, over-reliance on herbicides with similar modes of action has resulted in the evolution of herbicide-resistant weeds. The maximum number of herbicide-resistant were already reported in different crops such as wheat, maize, rice, soybean, spring barley, canola, cotton etc. Such issues suggest the need to develop different weed management options, and to consider the potential for integrating them with herbicide use. Thus, new herbicides with different modes of action are needed to manage herbicide-resistant weeds.

Pyroxasulfone is a pre-emergence herbicide that inhibits the production of very-long-chain fatty acid (VLCFA) synthesis by interfering with elongation of the C18 chains, which are normally catalyzed by VLCFA elongases. The formation of cell membranes and waxy cuticle materials within developing plant tissue is also severely affected by VLCFAs. Pyroxasulfone enters target plants through root-uptake or via the apical meristem and causes inhibition of shoot elongation after seed germination. It is a selective herbicide that primarily efficacious against annual grasses, sedges and provides control over annual broadleaf weeds.

Pyroxasulfone is chemically known as 3-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl] methane sulfonyl}-5,5-dimethyl-4,5-dihydro-1,2-oxazole, and has the following structure:

Topramezone is post-emergence herbicide, used for the treatment of broadleaf weeds and grasses. It is a potent inhibitor of 4-hydroxyphenylpyruvate dioxygenase (HPPD) that rapidly metabolizes to non-active substances. Inhibitors of 4-hydroxyphenylpyruvate dioxygenase (HPPD) prevent plant carotenoid pigment formation, which in turn leads to chlorophyll degradation. This mode of action provides weed-control for various crops.

Topramezone is chemically known as [3-(4, 5-dihydro-isoxazol-3-yl)-4-methylsulfonyl-2-methyl phenyl] (5-hydroxy-1-methyl-1H-pyrazol-4-yl) methanone], and has the following structure:

Tembotrione is a broad-spectrum early and mid-post-emergence herbicide that belongs to the tri-ketone class of herbicides. It acts by inhibiting 4-hydroxyphenylpyruvate dioxygenase (HPPD), which leads to chlorophyll destruction by photo-oxidation and causes bleaching of emerging foliar tissue.

Tembotrione is chemically known as 2-{2-chloro-4-(methyl sulfonyl)-3-[(2, 2, 2-trifluoroethoxy) methyl] benzoyl} cyclohexane-1,3-dione, and has the following structure:

Cyhalofop-butyl is a post-emergence, aryloxyphenoxypropionate herbicide, used in controlling grass weeds. Its mode of action involves inhibition of acetyl-coenzyme A carboxylase (ACCase) biosynthesis. Grass weed control is difficult to achieve in a grass crop. However, Cyhalofop-butyl is a selective herbicide that makes controlling difficult to manage weeds possible without damaging crops in which it is applied.

Cyhalofop-butyl is chemically known as 2-Butyl-(R)-2-[4(4-cyano-2-fluorophenoxy)-5 phenoxy] propionate, and has the following structure:

Mesotrione is used as a selective herbicide for the pre-emergence and post-emergence control of a wide range of broad-leaved and grass weeds. It is used for controlling crabgrass, goosegrass, barnyard grass, and yellow foxtail. This herbicide can also control several species of broadleaf weeds, as well as creeping bent grass, nimble will, and nutsedge in turf.

Mesotrione is chemically known as 2-[4-(Methyl sulfonyl)-2-nitrobenzoyl] cyclohexane-1,3-dione, and has the following structure:

Halosulfuron-methyl is a sulfonylurea post-emergence herbicide used to control some annual and perennial broad-leaved weeds and sedges in a range of crops, established landscape woody ornamentals and turf-grass. It is systemic and selective, and acts as an inhibitor of aceto-hydroxy acid synthase (AHAS) restricting the biosynthesis of the essential amino acids, valine and isoleucine, thus restricting plant /weed growth.

Halosulfuron-methyl is chemically known as Methyl 3-chloro-5-{[(4,6-dimethoxypyrimidin-2-yl) carbamoyl]sulfamoyl}-1-methyl-1H-pyrazole-4-carboxylate, and has the following structure:

Ametryn is a thiotriazine selective systematic herbicide absorbed principally through the roots, but also through the foliage, translocated acropetally in the xylem and accumulated in the apical meristems and leaves. It acts by binding to the plastoquinone-binding protein in photosystem II, inhibiting electron transport. It is effective against annual broadleaf weeds/grasses and used for pre-emergence and post-emergence control of both monocotyledonous and dicotyledonous weeds in corn, sugarcane, banana, pineapple, and non-crop areas.

Ametryn is chemically known as N2-ethyl-N4-isopropyl-6-methylthio-1, 3, 5-triazine-2, 4-diamine, and has the following structure:

Propaquizafop is an aryloxyphenoxypropionate herbicide primarily used for post emergence control of weeds. The mode of action of propaquizafop involves inhibition of the plastid acetyl coenzyme A carboxylase (ACCase), which is a key enzyme in fatty acid biosynthesis. Propaquizafop is used for selective weed control in many broadleaf crops such as sugar beet, rapeseed, soybeans, sunflower, vegetables, fruit trees, vineyards, forestry and the like. Propaquizafop is quickly absorbed by the leaves and translocated from the foliage to the growing points of the leaves and roots of the sprayed weeds.

Propaquizafop is chemically known as (R)-2-((propan-2-ylideneamino) oxy)ethyl 2-(4-((6- chloroquinoxalin-2-yl)oxy)phenoxy)propanoate, and has the following structure:

Penoxsulam is a triazolo pyrimidine sulfonamide herbicide, which is a post-germination herbicide having a broad-spectrum usage in paddy field. It can control and kill Echinochloa crusgalli and annual Cyperus weeds effectively, and it is effective against a variety of leafy weeds. Penoxsulam primarily works by inhibiting the enzyme acetolactate synthase (ALS) which disrupts the biosynthesis of these amino acids leading to the death of weeds.

Penoxsulam is chemically known as 2-(2,2-Difluoroethoxy)-N-(5,8-dimethoxy-[1,2,4] triazolo[1,5-c]pyrimidin-2-yl)-6-(trifluoromethyl)benzenesulfonamide, and has the following structure:

The above compounds/ingredients are individually known for their herbicidal effects. Some combination formulations of Pyroxasulfone are also known in the art.

US2018368400 relates to synergistic herbicidal composition comprising Pyroxasulfone, Topramezone and Atrazine for controlling the growth of undesirable plants. However, it is mentioned in US’400 that atrazine is prone to be moved to deep layer of soil by rainfall, therefore it is effective to certain weeds root deeply, but it is easy to produce toxic substance. As persistence of Atrazine in soil is very long, it is not recommended to increase its application rate randomly, especially in the arid areas, in case it causes harm to post-harvest crops.

CN111685122 belongs to ternary weeding composition containing ingredient A terbuthylazine, ingredient B pyroxasulfone and ingredient C selected from one of topramezone and tembotrione. However, it is mentioned in CN’122 that terbuthylazine is more effective against broad-leaved weeds than grass weeds, but less effective against perennial weeds.

US2022167622 directed to an aqueous composition comprising a mixture of epyrifenacil, mesotrione and pyroxasulfone for controlling weeds. It is disclosed in US’622 that Epyrifenacil is difficult to formulate in aqueous compositions.

US2021120820 discloses an agricultural mixture of pyroxasulfone, mesotrione and clopyralid for controlling weeds. However, drawbacks of clopyralid includes particularly damaging to peas, tomatoes, and sunflowers, and can render potatoes, lettuce, and spinach inedible. It also does not affect grasses.

CN108184883 relates to herbicide composition with pyroxasulfone, isoproturon and halosulfuron-methyl as active ingredients. However, Isoproturon produces a carcinogenic metabolite, that negatively affects the environment,

IN202141050386 discloses herbicidal composition comprising a mixture of pyroxasulfone, diclosulam and chlorimuron-ethyl. Said herbicidal composition allows efficient and reliable control of grass and broadleaf weeds in field with sufficiently long herbicidal activity in order to achieve control of the weeds over a sufficient long time period. However, the long-term application of chlorimuron-ethyl has led to residues in farmland soil and irrigation water, which disturb the growth of sensitive succeeding crops and other non-target plants.

IN202241047016 relates to a synergistic herbicidal composition comprising of Sulfosulfuron and Pyroxasulfone having improved stability and superior bio-efficacy compared to individual formulations. However, sulfosulfuron is slow-killing herbicide and it will take longer time period to show the effectiveness.

As stated above, the combination formulations of Pyroxasulfone in the art have certain disadvantages. Even though different herbicidal combinations have been developed still it is not always possible to control the difficult unwanted weeds. Also, cases of herbicide-resistant weeds have become increasingly common. Thus, there still remains a need in the agriculture for new herbicidal combinations and methods that provide longer control over unwanted plants/weeds in crops.

Object of the Invention:
Thus it is an object of the present invention to provide a synergistically effective herbicidal formulation comprising a combination of pre- and post-emergence selective herbicides with different mode of action that overcome the drawback of herbicide-resistant weed and exhibit synergy over single ingredient formulation.

Further object of the present invention is to effectively control and remove the broad spectrum of undesirable weeds and vegetation in agricultural as well as non-agricultural land for a longer period of time.

Accordingly, the main object of the present invention is to provide a synergistic herbicidal formulation comprising; (A) Pyroxasulfone; (B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione; and (C) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam along with one or more agrochemically acceptable adjuvants/excipients, for effective control or removal of broadleaf weeds, narrow-leaf weeds, turf weeds, sedges and annual and perennial grasses in agricultural as well as non-agricultural land.

Another object of the present invention is to provide a synergistic herbicidal formulation that can be easily prepared in different formulation types.

Yet another object of present invention is to provide a synergistic herbicidal formulation that can be applied as pre-emergent and post-emergent treatment.

Yet another object of the present invention is to provide a synergistic herbicidal formulation that exhibits synergy over individual/solo ingredients in terms of enhanced herbicidal activity for controlling unwanted plants/weeds.

Yet another object of the present invention is to provide a method of effective removal or control of weeds and growth of undesirable vegetation in agricultural as well as non-agricultural land by applying synergistic herbicidal formulation of the present invention.

Yet another object of the present invention is to provide method of effective removal or control of variety of weeds and undesirable vegetation in crops/fruits/vegetables by applying synergistic herbicidal formulation of the present invention.

Yet another object of present invention is to provide a synergistic herbicidal formulation that provide enhanced weed control, reduce crop damage and improved crop health thereby increasing crop yield.

Yet another object of present invention is to provide a synergistic herbicidal formulation that is environmentally safe, possesses broad spectrum weed control efficacy and is less toxic.

Summary of the Invention:
In accordance with the above objective, in a preferred aspect, the present invention describe a synergistic herbicidal formulation comprising; (A) Pyroxasulfone; (B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione; and (C) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam along with one or more agrochemically acceptable adjuvants/excipients.

In a preferred aspect, the present invention describes a synergistic herbicidal formulation comprising;
(A) Pyroxasulfone in an amount of 2 to 45%;
(B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40%;
(C) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70%;
along with one or more agrochemically acceptable adjuvants/excipients in an amount of 0.1 to 40% by weight of total formulation.

In another aspect, the present invention describes a process for preparation of said synergistic herbicidal formulation.

In another aspect, the present invention describes different formulation types of said synergistic herbicidal formulation.

In another aspect, the present invention describes a synergistic herbicidal formulation that exhibits enhanced herbicidal activity over individual/solo ingredient formulations in terms of controlling unwanted weeds and vegetation in crops/plants.

In another aspect, the present invention describes a synergistic herbicidal formulation that demonstrate synergy over individual/solo ingredient formulations in terms of controlling unwanted weeds and vegetation in crops/plants.

In another aspect, the present invention describes a method of effective removal or control of weeds and growth of undesirable vegetation in agricultural as well as non-agricultural land by applying synergistic herbicidal formulation of the present invention.

In another aspect, the present invention describes a method of effective removal or control of weeds and growth of undesirable vegetation in crops/fruits/vegetables by applying synergistic herbicidal formulation of the present invention.

Detailed Description of the Invention:
The present invention will now be described in detail in connection with certain embodiments, so that various aspects thereof may be fully understood and appreciated.

The phrase ‘Pre-emergent herbicides’ used in the present invention refers to the herbicides which remain in the soil and kill the weed seed soon after it germinates.

The phrase ‘Post-emergent herbicides’ used in the present invention refers to the herbicides which kill the weeds, when they start coming out of the ground.

The phrase ‘Selective herbicides’ used in the present invention refers to the herbicide which kill the weeds, but does not kill the valuable plant.

The present invention discloses a synergistic herbicidal formulation comprising; (A) Pyroxasulfone; (B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione; and (C) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam along with one or more agrochemical acceptable adjuvants/excipients.

The present invention discloses a synergistically effective herbicidal formulation comprising combination of pre- and post-emergence selective herbicides with different mode of action; wherein, Pyroxasulfone is pre-emergent herbicides; Mesotrione and Ametryn are pre-emergent and post-emergent herbicides; and the remaining Topramezone, Tembotrione, Cyhalofop-butyl, Halosulfuron-methyl, Propaquizafop and Penoxsulam are post-emergent herbicides. The said combination of pre- and post-emergence herbicides effectively control and remove the broad spectrum of undesirable weeds and vegetation in agricultural as well as non-agricultural land.

The active ingredients in the present synergistic formulation are selective herbicides that controls weed species while leaving the desired crop relatively unharmed. The selective herbicides work by targeting specific metabolic processes that plants rely on to survive. Not all plants have the same metabolic processes, hence by using a selective herbicide which is safe, the control over undesirable weeds and vegetation growth whilst sparing the crop is achieved.

In a preferred embodiment, the present invention disclose a synergistic herbicidal formulation comprising;
(A) Pyroxasulfone in an amount of 2 to 45%;
(B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40%;
(C) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70%;
along with one or more agrochemically acceptable adjuvants/excipients in an amount of 0.1 to 40% by weight of total formulation.

The agrochemically acceptable adjuvants/excipients of the present synergistic herbicidal composition is selected from dispersing agents/dispersants, wetting agents, emulsifying agents/ emulsifiers, stabilizing agents/stabilizers, thickening agents/thickeners, solubilizing agents/ solubilizers, binding agents/binders, buffering agents, structuring agents, thickener and emulsion stabilizers, emulsification and dispersion, stabilizer cum dispersing agents, surfactants, anti-freezing agents, anti-foaming agents, anti-caking agents, biocides/preservatives, rheology modifiers, solvents, bio-solvents, carrier agents/carriers, inerts and fillers/continues phase thereof.

Suitable dispersing agent/dispersant is selected from alkylnaphthalene sulfonate condensate, dodycylbenzenesulfonic acid sodium salt, octyl phenol ethoxylate, nonionic tristyryphenol, sodium lignosulfonate, sodium lignosulfonate ethoxylated, polyalkoxylated butyl ether, low degree sulfonated kraft lignin, nonionic ethopropoxylated polyarylphenol, styrene acrylic polymer, acrylic copolymer, ethoxylated sorbitan ester, lignosulphonic acid sodium salt, calcium salt of alkyl benzene sulphonate, tristyrylphenol ethoxylate phosphate ester, sodium polycarboxylate, methyl naphthalin sulphonate sodium salt, acrylate copolymer, anionic surfactant of naphthalene sulphonic acid condensate, lignosulfonate sodium salts sulfomethylated and sodium lignosulphonate. The dispersing agent/dispersant is present in an amount of 0.1 to 12% of the total weight of the formulation.

Suitable wetting agent is selected from lauryl alchohol condensate, mixture of mineral oils and alkyl aryl ether, low degree sulfonated kraft lignin, hydrophilic ethpropoxylated polyarylphenol, nonionic block copolymer, sodium polycarboxylate, calcium alkylaryl sulphonate, sodium dodecyl sulphate, sodium methyl cocoyl taurate, sodium isopropyl naththanene sulphonate, lauryl alcohol condensate, mixture of mineral oils and alkyl aryl ether, low degree sulfonated kraft lignin and sodium polycarboxylate. The wetting agent is present in an amount of 0.2 to 5% of the total weight of the formulation.

Suitable emulsifying agent/emulsifier is selected from tristyrylphenol ethoxylated, calcium dodecylbenzene sulphonate, blend of calcium alkyl benzene sulphonate and alkoxy alkyl ether, tristrylphenol ethoxylate phosphate ester, fatty acids polycondensed, alkyl benzene sulfonate calcium salt, dodycylbenzenesulfonic acid sodium salt, octyl phenol ethoxylate, nonionic tristyryphenol and linear calcium dodecylbenzine sulphonate. The emulsifying agent/emulsifier is present in an amount of 0.1 to 15% of the total weight of the formulation.

Suitable stabilizing agent/stabilizer is selected from Propane-1,2 Diol, Propane- 1,2,3-triol, propylene glycol, fatty acids polycondensed, sodium polyacrelate, polyacrylate copolymer, synthetic polymer, polyvinylpyrrolidone, 1,2-Dihydroxyethane and ricinoleic acid triglyceride. The stabilizing agent/stabilizer is present in an amount of 0.1 to 6% of the total weight of the formulation.

Suitable thickening agent/thickener is selected from sodium polyacrylate, disaccharide composed, polysaccharide and SiO2 anhydrous. The thickening agent/thickener is present in an amount of 0.1 to 1% of the total weight of the formulation.

Suitable solubilizing agent/solubilizer is selected from benzyl acetate, Solvesso 200, polyacrylate copolymer. The solubilizing agent/solubilizer is present in an amount of 1 to 12 % of the total weight of the formulation.

Suitable binding agent/binder is selected from polymeric carbohydrate, polyvinylpyrrolidone and polyvinyl alcohol. The binding agent/binder is present in an amount of 0.1 to 1.5% of the total weight of the formulation.

Suitable buffering agent is selected from soda ash, sodium carbonate ammonia, magnesium carbonate and acetic acid. The buffering agent is present in an amount of 0.1 to 1% of the total weight of the formulation.

Suitable structuring agent is selected from heteropolysaccharide and xanthan gum. The structuring agent present in an amount of 0.10 to 0.25% of the total weight of the formulation.

Suitable thickener and emulsion stabilizer is selected from sodium polyacrylate, synthetic polymer and polyvinylpyrrolidone. The thickener and emulsion stabilizer is present in an amount of 0.1 to 3% of the total weight of the formulation.

Suitable emulsification and dispersion agent is selected from dodycylbenzene sulfonic acid sodium salt, calcium salt of alkyl benzene sulphonate, octyl phenol ethoxylate, multiple nonionic tristyryphenol and tristyrylphenol ethoxylate phosphate ester. The emulsification and dispersion agent is present in an amount of 1 to 4% of the total weight of the formulation.

Suitable stabilizer cum dispersing agent is selected from sodium lignosulfonate ethoxylated, poly alkoxylated butyl ether and low degree sulfonated kraft lignin. The stabilizer cum dispersing agent is present in an amount of 0.1 to 2% of the total weight of the formulation.

Suitable surfactant is selected from acrylic polymer, C12-15 ethoxylated alcohols and acrylic polymer. The surfactant is present in an amount of 0.1 to 5% of the total weight of the formulation.

Suitable anti-freezing agent is selected from ricinoleic acid triglyceride, propane-1,2 diol, propane-1,2,3-triol, 1,2-dihydroxyethane, fatty acids polycondensed and propylene glycol. The anti-freezing agent is present in an amount of 0.1 to 6% of the total weight of the formulation.

Suitable anti-foaming agent is selected from polydimethyl siloxane, deformer, silicon deformer and polydimethyl siloxane. The anti-foaming agent is present in an amount of 0.1 to 2% of the total weight of the formulation.

Suitable anti-caking agents is precipitated silica, silicon dioxide, calcium silicate, magnesium stearate, sodium aluminosilicate, potassium aluminium silicate, tricalcium phosphate, sodium ferrocyanide, calcium carbonate, diatomaceous earth and sodium bicarbonate. The anti-caking agent is present in an amount of 0.2 to 1.5% of the total weight of the formulation.

Suitable biocide/preservative is selected from 1,2-benzisothiazolin-3-one; Proprietary mixture of 1,2 benziso thiazolin- 3-one, sodium hydroxide and dipropylene glycol in aqueous media. The biocide/preservative is present in an amount of 0.1 to 0.8% of the total weight of the formulation.

Suitable rheology modifier is selected from bentonite clay, xanthan gum, polyvinyl alcohol and polysaccharide. The rheology modifier is present in an amount of 0.1 to 2% of the total weight of the formulation.

Suitable solvent is selected from aromatic hydrocarbon, heavy aromatic naphtha, N-Methyl-2-pyrrolidone, mixture of aromatic hydrocarbons (Solvent C-9), Solvesso 200, Solvesso 150, soya methyl ester, benzyl acetate and heavy aromatic naphtha. The solvent is present in an amount of 5 to 30% of the total weight of the formulation.

Suitable bio-solvent is soya methyl ester, ethanol, isopropyl ester, poly-p-phynele sulphide, and ethyl lactate. The bio-solvent is present in an amount of 30 to 40% of the total weight of the formulation.

Suitable carrier agent/carrier is selected from ricinoleic acid triglyceride, dioctahedral phyllosilicate clay. The carrier agent/carrier is present in an amount of 0.20 to 40% of the total weight of the formulation.

Suitable inert is selected from kaolinite, hydrated magnasium silicate, talc, chalk, quartz, calcite and talcum. The inert is present in an amount of 5 to 20% of the total weight of the formulation.

Suitable filler/continuous phase is selected from aqua/water, fume silica, kaolin and china clay. The filler is present in an amount of 1 to 40% of the total weight of the formulation.

In a preferred embodiment, the present invention discloses a synergistic herbicidal formulation that can be formulated as but not limited to Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW) and the like.

Accordingly, in an embodiment, the present invention discloses Suspension Concentrate (SC) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(g) buffering agent in an amount of 0.1 to 1% (w/w);
(h) anti-freezing agent in an amount of 0.1 to 6% (w/w);
(i) anti-caking agent in an amount of 0.2 to 1.5% (w/w);
(j) thickening agent in an amount of 0.1 to 1% (w/w);
(k) surfactant in an amount of 0.1 to 5% (w/w);
(l) biocide/preservative in an amount of 0.1 to 0.8% (w/w);
(m) rheology modifier in an amount of 0.1 to 2% (w/w);
(n) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

In another embodiment, the present invention discloses Suspo-emulsion (SE) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) emulsifying agent in an amount of 0.1 to 15% (w/w);
(g) binding agent in an amount of 0.1 to 1.5% (w/w);
(h) buffering agent in an amount of 0.1 to 1% (w/w);
(i) thickening agent in an amount of 0.1 to 1% (w/w);
(j) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(k) anti-caking agent in an amount of 0.2 to 1.5% (w/w);
(l) anti-freezing agent in an amount of 0.1 to 6% (w/w);
(m) structuring agent in an amount of 0.10 to 0.25% (w/w);
(n) thickener and emulsion stabilizer in an amount of 0.1 to 3% (w/w);
(o) emulsification and dispersion in an amount of 1 to 4% (w/w);
(p) stabilizer cum dispersing agent in an amount of 0.1 to 2% (w/w);
(q) biocide/preservative in an amount of 0.1 to 0.8% (w/w);
(r) rheology modifier in an amount of 0.1 to 2% (w/w);
(s) solvent in an amount of 5 to 30% (w/w);
(t) carrier agent in an amount of 0.20 to 40% (w/w);
(u) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

In another embodiment, the present invention discloses Water dispersible granule (WDG/WG) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) buffering agent in an amount of 0.1 to 1% (w/w);
(g) binding agent in an amount of 0.1 to 1.5% (w/w);
(h) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(i) anti-caking agent in an amount of 0.2 to 1.5% (w/w);
(j) carrier agent in an amount of 0.20 to 40% (w/w);
(k) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

In another embodiment, the present invention discloses Wettable Powder (WP) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(g) anti-caking agent in an amount of 0.2 to 1.5% (w/w);
(h) carrier agent in an amount of 0.20 to 40% (w/w);
(i) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

In another embodiment, the present invention discloses Emulsifiable concentrate (EC) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) binding agent in an amount of 0.1 to 1.5% (w/w);
(g) emulsifying agent in an amount of 0.1 to 15% (w/w);
(h) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(i) anti-freezing agent in an amount of 0.1 to 6% (w/w);
(j) thickening agent in an amount of 0.1 to 1% (w/w);
(k) surfactant in an amount of 0.1 to 5% (w/w);
(l) stabilizer in an amount of 0.1 to 6% (w/w);
(m) thickener and emulsion stabilizer in an amount of 0.1 to 3% (w/w);
(n) biocide/preservative in an amount of 0.1 to 0.8% (w/w);
(o) rheology modifier in an amount of 0.1 to 2% (w/w);
(p) solvent in an amount of 5 to 30% (w/w);
(q) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

In another embodiment, the present invention discloses Oil dispersion (OD) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) emulsifying agent in an amount of 0.1 to 15% (w/w);
(g) binding agent in an amount of 0.1 to 1.5% (w/w);
(h) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(i) anti-freezing agent/ stabilizer in an amount of 0.1 to 6% (w/w);
(j) thickener and emulsion stabilizer in an amount of 0.1 to 3% (w/w);
(k) surfactant in an amount of 0.1 to 5% (w/w);
(l) biocide/preservative in an amount of 0.1 to 0.8% (w/w);
(m) rheology modifier in an amount of 0.1 to 2% (w/w);
(n) solvent in an amount of 5 to 30% (w/w);
(o) carrier agent in an amount of 0.20 to 40% (w/w);
(p) bio-solvent in an amount of 30 to 40% (w/w) of the total weight of the formulation.

In one embodiment, the present invention discloses a process for preparation of synergistic herbicidal formulation by mixing the active ingredient and excipients/additives in an appropriate amount to formulate a desired dosage form.

Accordingly, in another embodiment, the present invention discloses a process for preparation of suspension concentrate (SC) comprises;
(a) Charging DM water in clean and dry reactor fitted with stirrer followed by adding all excipients one by one under stirring for 30 min. under ambient temperature and mixing to completely homogenize.
(b) adding all active ingredients one by one slowly in step (a) under stirring and mixing to completely homogenize; and
(c) passing the homogenized slurry of step (b) through beadmill to achieve desire particle size of SC formulation.

In another embodiment, the present invention discloses a process for preparation of suspo-emulsion (SE) comprises;
(a) Charging Propaquizafop / Cyhalofop-butyl / Topramezone in solvent and dissolving completely in reactor-1;
(b) adding thickener and emulsion stabilizer in step (a) followed by mixing and stirring for 30 min. at more than 800 rpm to obtain EW form;
(c) charging water in reactor-2 fitted with stirrer and adding all the remaining excipients one by one under stirring followed by mixing for 30. min under ambient temperature to obtain complete homogenize slurry;
(d) adding remaining two active ingredients (Pyroxasulfone and Tembotrione / Mesotrione / Halosulfuron-methyl / Ametryn / Penoxsulam) one by one slowly in step (c) under stirring and mixing to obtain complete homogeneity;
(e) bead milling the slurry of step (d) to achieve desire particle size to obtain SC form; and
(f) transferring SC form obtain in step (e) into EW form of step (b) followed by homogenizing the mixture completely to obtain final SE form.

In another embodiment, the present invention discloses a process for preparation of water dispersible granule (WDG/WG) comprising;
(a) Charging all excipients and active ingredients in pre-blender and mixing for 30 min. under ambient temperature to complete homogenized;
(b) grinding the pre-blending material of step (a) to achieve desire particle size followed by post blending to obtain homogenize milled premix;
(c) charging milled premix of step (b) in dough maker to prepare dough followed by spraying DM water under stirring to obtain proper dough; and
(d) charging dough of step (c) in extruder and collecting granules and charging in dryer above 50°C temperature to obtain WDG formulation.

In another embodiment, the present invention discloses a process for preparation of Wettable Powder (WP) comprises;
(a) Charging all excipients and active ingredients in pre-blender and mixing for 30 min. under ambient temperature to complete homogenized; and
(b) grinding the pre-blending material of step (a) to achieve desired particle size followed by post blending the homogenize milled premix to obtain WP formulation.

In another embodiment, the present invention discloses a process for preparation of Emulsion Concentrate (EC) comprises;
(a) charging solvent in reactor fitted with stirrer and adding all three active ingredients one by one under stirring and dissolve completely; and
(b) adding stabilizer and emulsifier to step (a) and homogenize the mixture completely to obtain EC formulation.

In another embodiment, the present invention discloses a process for preparation of Oil Dispersion (OD) comprises;
(a) Charging carrier agent in reactor fitted with high-speed stirrer and adding wetting agent, dispersing agent, emulsifier and preservative one by one;
(b) adding all three active ingredients one by one slowly in step (a) under stirring and mixing thru high speed stirring to complete homogenized;
(c) adding rheology modifier to step (b) and stirring to obtain homogenize mass as OD formulation.

In another embodiment, the present invention describes a synergistic herbicidal formulation with particle size of active ingredients is maintained between 0.5 to 50 micron.

In another embodiment, the present invention describes a synergistic herbicidal formulation that can be applied as pre-emergent and post-emergent treatment.

In another embodiment, the present invention describes a synergistic herbicidal formulation that is environmentally safe, possesses broad spectrum weed control efficacy and is less toxic.

In another embodiment, the present invention describes a synergistic herbicidal formulation that is non-phytotoxic to crop/plants.
In another embodiment, the present invention discloses a method of effective removal or control of growth of weeds and undesirable vegetation including but not limited to, broadleaf weeds, narrowleaf weeds, turf weeds, sedges and annual and perennial grasses in agricultural as well as non-agricultural land by applying synergistic herbicidal formulation of the present invention comprising; (A) Pyroxasulfone in an amount of 2 to 45%; (B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop and Mesotrione in an amount of 0.5 to 40%; (C) at least one herbicide selected from Halosulfuron, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% along with one or more agrochemically acceptable adjuvants/excipients in an amount of 0.1 to 40% by weight of total formulation.

The broadleaf weeds include but are not limited to, Giant Pigweed/Black Pigweed (Trianthema spp), Prostrate pigweed (Amaranthus spp.), Chickweed (Stellaria media), Dandelion (Taraxacum officinale), Florida betony (Stachys floridana), Japanese clover (Lespedeza striata), broadleaf plantain (Plantago major), Common vetch (Vicia sativa) and the like.

The grass weeds include but are not limited to, Wild rice (Echinochloa colonum), Bermuda grass (Cynodon dactylon), Crabgrass (Digitaria spp), Quackgrass, Doveweed, Dallisgrass, Nutsedge, Bluegrass (Poa annua), Goosegrass and the like.

The turf weeds include but are not limited to annual bluegrass, birdsfoot trefoil, black medic, buckhorn plantain, common mallow, common purslane, field paspalum, fountain grass, goose grass, ground ivy, henbit, large crab grass, mouse ear chickweed, nimble will, orchard grass, pineapple weed, prostrate knotweed, prostrate spurge, purple deadnettle, quack grass, roughstalk blue grass, smooth crabgrass, tall fescue, white cover, wild garlic, wild violets, yellow nutsedge and the like.

The sedges include but are not limited to annual sedge, green kyllinga, purple nutsedge, yellow nutsedge, Cyperus alternifolius (Umbrella Palm), Cyperus compressus (Poor Land Flat Sedge), Cyperus difformis, Cyperus exaltatus, Cyperus haspan, Cyperus iria, Cyperus laevigatus, Cyperus rotundus (Common Nut Sedge, Moth), Cyperus squarrosus, Fimbristylis ovate, Kyllinga nemoralis (White Water Sedge), Pycreus polystachyos and the like.

The annual and perennial grasses include but are not limited to, annual blue-eyed grass, annual bluegrass, annual ryegrass, bahiagrass, bermuda grass, blue-eyed grass, common dayflower, crowfoot grass, crow-poison, dallis grass, dove weed, goose grass, johnson grass, jungle rice king ranch bluestem, large crabgrass, ohio spiderwort, prairie nymph, prairie spiderwort, red sprangletop, rescuegrass sandbur, smooth crabgrass, smutgrass, spring starflower, wild onion and the like.

The non-agricultural land include but are not limited to, turfgrass, pastures, grasslands, rangelands, fallow land, aquatic settings, wildlife management areas or rangeland.

In another embodiment, the present invention describes method of effective removal or control of growth of weeds and undesirable vegetation in crops/fruits/vegetables by applying synergistic herbicidal formulation comprising; (A) Pyroxasulfone in an amount of 2 to 45%; (B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop and Mesotrione in an amount of 0.5 to 40%; (C) at least one herbicide selected from Halosulfuron, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% along with one or more agrochemically acceptable adjuvants/excipients in an amount of 0.1 to 40% by weight of total formulation.

The crops include but are not limited to soyabean (Glycine max), rice/paddy (Oryza sativa), sugarcane (Saccharum officinarum), corn/maize (Zea mays), Sorghum (Sorghum bicolor), Pearl millet (Pennisetum glaucum), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Tea (Camellia sinensis), Coffea (Coffea Arabica) and the like.

The fruits include but are not limited to Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum), Sapota (Manilkara zapota), Coconut (Coco nucifera) and the like.

The vegetables include but are not limited to solanaceous vegetables such as eggplant, tomato, pimento, popper, potato, etc., cucurbit vegetables such as cucumber, pumpkin, zucchini, water melon, melon, squash, etc., cruciferous vegetables such as radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower, etc., asteraceous vegetables such as burdock, crown daisy, artichoke, lettuce, etc, liliaceous vegetables such as green onion, onion, garlic, and asparagus, ammiaceous vegetables such as carrot, parsley, celery, parsnip, etc., chenopodiaceous vegetables such as spinach, swiss chard, etc., lamiaceous vegetables such as Perilla frutescens, mint, basil, etc. strawberry, sweet potato, Dioscorea japonica, colocasia, and the like.

In another embodiment, the present invention describes a synergistic herbicidal formulation that provide enhanced weed control, reduce crop damage and improved crop health thereby increasing crop yield.

Examples:
The present invention is further illustrated by the following examples. The different aspects and embodiments of the present invention may become more apparent from the examples set forth herein below. These examples describe possible preferred embodiments for illustrative purposes only, but they do not limit the scope of the invention.

Example 1 to 11: Formulation 1 - Pyroxasulfone + Mesotrione + Propaquizafop

Example No. 1 2 3 4 5 6 7 8 9 10 11
Formulation Type SC SC SC OD OD OD EC EC EC EC SE
Ingredients Quantity (g) Role of Ingredient
Pyroxasulfone (Purity: 98.0% w/w) 21.0 18.2 23.3 21.0 18.2 21.0 21.0 18.2 23.3 21.0 21.0 Active Ingredient
Mesotrione
(Purity: 97.5% w/w) 35.0 33.2 36.5 35.0 33.2 35.0 35.0 33.2 36.5 35.0 35.0 Active Ingredient
Propaquizafop
(Purity: 98.0% w/w) 8.0 8.2 10.8 8.0 8.2 8.0 8.0 8.2 10.8 8.0 8.0 Active Ingredient
Alkylnaphthalene sulfonate condensate 1.7 ---- ---- ---- ---- ---- 2.7 ---- ---- ---- ---- Dispersing agent
Sodium Polycarboxylate ---- 2.4 ---- ---- ---- ---- ---- 2.4 2.8 ---- ---- Dispersing agent
Acrylic copolymer ---- ---- 1.9 ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Anionic surfactant of Naphthalene sulphonic acid condensate 0.4 ---- 0.3 ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Lignosulfonate sodium salts sulfomethylated ---- 0.3 ---- ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Nonionic methoxypropoxylated polyarylphenol ---- ---- ---- ---- ---- 1.8 ---- ---- ---- ---- ---- Dispersing agent
Sodium dodecyl sulphate ---- ---- ---- ---- ---- ---- 1.1 ---- ---- ---- ---- Wetting agent
Sodium Methyl Cocoyl Taurate ---- ---- ---- ---- ---- ---- ---- 1.6 ---- ---- ---- Wetting agent
Sodium isopropyl naththanene sulphonate 1.1 ---- ---- ---- ---- ---- ---- ---- 1.4 ---- ---- Wetting agent
Calsium alkylaryl sulphonate ---- 1.5 ---- ---- ---- ---- ---- ---- ---- ---- ---- Wetting agent
Hydrophilic methoxypropoxylated polyarylphenol ---- 1.2 3 Wetting agent
Lauryl alcohol condensate ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.50 Wetting agent
Tristyrylphenol ethoxylated ---- ---- ---- 1.8 ---- ---- 0.5 ---- ---- ---- ---- Emulsifying agent
Calcium dodecylbenzene sulphonate ---- ---- ---- ---- 1.5 ---- ---- 0.5 0.3 ---- ---- Emulsifying agent
Blend of Calcium alkyl benzene sulphonate and alkoxy alkyl ether ---- ---- ---- ---- ---- ---- ---- ---- ---- 12 ---- Emulsifying agent
Tristrylphenol ethoxylate phosphate ester ---- ---- ---- ---- ---- 2 ---- ---- ---- ---- ---- Emulsifying agent
Fatty acids, polycondensed ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.20 Emulsifying agent
Polyvinyl pyrilidone ---- ---- ---- 0.5 0.3 ---- 0.8 0.5 0.7 ---- ---- Binding agent
Sodium Polyacrelate ---- ---- ---- ---- ---- ---- ---- ---- 0.2 ---- 0.40 Thickner and Emulsion stabilizer
Synthetic polymer ---- ---- ---- ---- ---- ---- 0.4 0.3 ---- ---- ---- Thickner and
emulsion stabilizer
1,2-Dihydroxyethane ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.5 ---- Stabilizer
Acrylic polymer ---- ---- ---- 0.5 ---- ---- ---- ---- 0.5 ---- ---- Surfactant
C12-15 ethoxylated Alcohols ---- ---- ---- ---- 0.7 ---- 0.3 0.3 ---- ---- Surfactant
Soda ash ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.25 Buffering agent
Dodycylbenzene sulfonic acid,
sodium salt ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 2.20 Emulsification and Dispersion
Solvesso 200 ---- ---- ---- ---- ---- ---- 11.0 ---- ---- ---- ---- Solvent / Solubilizer
Solvesso 150 ---- ---- ---- ---- ---- ---- ---- 12.0 10.0 ---- ---- Solvent
Aromatic hydrocarbon ---- ---- ---- 7.0 10.0 ---- ---- ---- ---- ---- 20.00 Solvent
Soya methyl ester ---- ---- ---- 25.7 26.9 ---- ---- ---- ---- ---- ---- Solvent
N-Methyl-2-pyrrolidone ---- ---- ---- ---- ---- ---- ---- ---- ---- 10.00 ---- Solvent
Mixture of aromatic hydrocarbons ---- ---- ---- ---- ---- ---- ---- ---- ---- 12.5 ---- Solvent
Sodium lignosulfonate Ethoxylated ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.20 Stabilizer cum dispersing agent
Polydimethyl siloxane 0.4 0.3 0.5 0.5 1.0 ---- 0.2 0.3 0.5 ---- 0.25 Anti-foaming agent
Propane-1,2 Diol 2.2 3.2 2.1 ---- ---- ---- ---- ---- ---- ---- ---- Anti-freezing agent/ Stabilizer
Propane- 1,2,3-triol ---- ---- ---- ---- ---- ---- 2.0 2.5 2.2 ---- ---- Anti-freezing agent/ Stabilizer
1,2-Benzisothiazoline-3-one 0.1 0.2 0.2 ---- ---- 0.1 0.1 0.1 0.2 ---- 0.10 Biocide/ Preservative
Bentonite clay ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- Rheology modifier
Xanthan gum 0.2 0.1 0.1 ---- ---- ---- 0.1 ---- ---- ---- ---- Rheology modifier
Polyvinyl alcohol ---- ---- ---- ---- ---- 2 ---- ---- ---- ---- ---- Rheology modifier
Sodium polyacrylate ---- ---- ---- ---- ---- ---- ---- 0.1 0.1 ---- ---- Thickening agent
Heteropolysaccharide ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.15 Structuring agent
Ricinoleic acid triglyceride ---- ---- ---- ---- ---- 27.1 ---- ---- ---- ---- 0.25 Carrier agent
Aqua/Water 30.0 32.4 23.1 ---- ---- ---- 16.8 19.8 10.6 ---- 9.5 Continues phase / Filler
Total 100g 100g 100g 100g 100g 100g 100g 100g 100g 100g 100g ----

Example 12 to 25: Formulation 2 - Pyroxasulfone + Tembotrione + Halosulfuron-methyl
Example No. 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Formulation Type WP WP WP WP WG WG WG WG SC SC SC SE SE SE
Ingredients Quantity (g) Role of Ingredient
Pyroxasulfone (Purity: 98.0% w/w) 23 21.7 24.6 23 23 21.7 24.6 23 23 21.7 23 23 21.7 23 Active Ingredient
Tembotrione
(Purity: 96.0% w/w) 22 19.9 24 22 22 19.9 24 22 22 19.9 22 22 19.9 22 Active Ingredient
Halosulfuron- methyl
(Purity: 97.0% w/w) 10 8.8 12 10 10 8.8 12 10 10 8.8 10 10 8.8 10 Active Ingredient
Anionic surfactant of Naphthalene sulphonic acid condensate ---- ---- ---- ---- ---- ---- ---- 5.3 ---- ---- ---- ---- ---- ---- Dispersing agent
Alkylnaphthalene sulfonate condensate 4.85 3.8 ---- ---- ---- 10 ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Sodium Poly carboxylate 1.2 ---- 3.5 ---- ---- ---- ---- ---- ---- 1.7 ---- ---- ---- ---- Dispersing agent
Acrylic copolymer ---- ---- ---- ---- 2.9 ---- 5.3 ---- 3.2 ---- 3.5 1.8 ---- ---- Dispersing agent
Styrene acrylic polymer ---- ---- ---- 2.5 ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Methyl naphthalin sulphonate sodium salt ---- ---- ---- 3.3 ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Lignosul phonic acid, sodium salt ---- ---- 4.4 ---- 3.3 ---- ---- ---- ---- 0.5 ---- ---- 0.8 ---- Dispersing agent
Lignosul fonate sodium salts sulfomethy lated ---- 2.3 ---- ---- ---- ---- ---- 2.8 ---- ---- ---- ---- ---- ---- Dispersing agent
Lauryl alcohol condensate ---- ---- ---- ---- ---- ---- ---- 2.6 ---- ---- ---- ---- ---- ---- Wetting agent
Sodium dodecyl sulphate 3.75 ---- ---- ---- ---- ---- ---- ---- ---- 1.5 ---- ---- 1.2 ---- Wetting agent
Sodium Methyl Cocoyl Taurate ---- ---- 2.5 ---- ---- ---- ---- ---- 1.8 ---- ---- 2.5 ---- ---- Wetting agent
Sodium isopropyl naththanene sulphonate ---- ---- ---- 1.4 2.4 ---- 3.4 ---- ---- ---- ---- ---- ---- ---- Wetting agent
Nonionic block copolymer ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 2.3 ---- ---- ---- Wetting agent
Hydrophilic methoxypropoxylated poly arylphenol ---- 2.7 ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- Wetting agent
Mixture of Mineral oils and Alkyl Aryl ether ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.2 Wetting agent
Tristyryl phenol ethoxylated ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.9 ---- ---- Emulsifying agent
Calcium dodecyl benzene sulphonate ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.4 0.3 Emulsifying agent
Sodium Polyacrelate ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.2 ---- ---- Thickner and Emulsion stabilizer
Synthetic polymer ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.3 2.1 Thickner and
emulsion stabilizer
Acrylic polymer ---- ---- ---- ---- ---- ---- ---- ---- ---- 3.0 ---- ---- ---- ---- Surfactant
Soda ash ---- ---- ---- ---- ---- ---- 0.2 ---- ---- ---- ---- ---- ---- ---- Buffering agent
Calcium salt of alkyl benzene sulphonate ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.5 ---- ---- ---- Emulsification and Dispersion
Benzyl acetate ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 10 ---- ---- Solvent / solubilizer
Solvesso 200 ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 8 ---- Solvent / Solubilizer
Mixture of aromatic hydrocarbons ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 15 Solvent
Poly alkoxylated butyl ether ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.35 0.26 1.6 Stabilizer cum dispersing agent
Polyacrylate copolymer ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.5 Liquid stabilizer
Octyl phenol ethoxylate ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.2 Emulsification and Dispersion
Polydimethyl siloxane ---- ---- ---- ---- 0.5 1 0.5 ---- 0.5 0.5 ---- 0.2 0.2 0.25 Anti-foaming agent
Deformer ---- ---- ---- ---- ---- ---- ---- 0.5 ---- ---- 0.2 ---- ---- ---- Anti-foaming agent
Polyvinyl pyrilidone ---- ---- ---- ---- ---- 1 --- 0.8 ---- ---- ---- ---- ---- ---- Binding agent
Polyvinyl alcohol ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.4 0.38 ---- Binding agent
Polymeric carbohydrate ---- ---- ---- ---- ---- ---- 0.4 ---- ---- ---- ---- ---- ---- ---- Binding agent
Precipitated silica ---- 1.3 ---- ---- 1.1 ---- ---- 1.4 ---- ---- ---- 0.5 0.7 ---- Anti-caking agent
Propane-1,2 Diol ---- ---- ---- ---- ---- ---- ---- ---- ---- 3.5 ---- 2 1.5 2.8 Anti-freezing agent/ Stabilizer
Propylene glycol ---- ---- ---- ---- ---- ---- ---- ---- 4.8 ---- ---- ---- ---- ---- Anti-freezing agent/ Stabilizer
1,2-Dihydroxyethane ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 2.2 ---- ---- ---- Anti-freezing agent
1,2-Benzisothiazoline-3-one ---- ---- ---- ---- ---- ---- ---- ---- 0.25 0.15 0.1 0.1 0.1 ---- Biocide/ Preservative
Proprietary mixture of 1,2 benziso thiazolin- 3-one; Sodium hydroxide and Dipropylene glycol in aqueous media ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.4 Biocide/ Preservative
Xanthan gum ---- ---- ---- ---- ---- ---- ---- ---- 0.18 ---- ---- 0.8 0.12 0.14 Rheology modifier
Sodium polyacrylate ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.18 ---- ---- ---- Thickening agent
Fume silica ---- ---- ---- ---- ---- 3 ---- ---- ---- ---- ---- ---- ---- ---- Filler
Kaolin 35.2 ---- ---- ---- ---- 34.6 ---- ---- ---- ---- ---- ---- ---- ---- Filler
Chinaclay ---- ---- ---- ---- 34.8 ---- 29.6 ---- ---- ---- ---- ---- ---- ---- Filler
Dioctahedral phyllosilicate clay ---- 39.5 29 37.8 ---- ---- ---- 31.6 ---- ---- ---- ---- ---- ---- Carrier agent
Aqua / Water ---- ---- ---- ---- ---- ---- ---- ---- 34.27 38.75 35.02 24.25 35.64 18.51 Continues phase / Filler
Total 100g 100g 100g 100g 100g 100g 100g 100 g 100g 100g 100g 100g 100g 100g ----

Example 26 to 37: Formulation 3 - Pyroxasulfone + Cyhalofop-butyl + Penoxsulam

Example No. 26 27 28 29 30 31 32 33 34 35 36 37
Formulation Type SC SC SC SC SE SE SE EC EC EC OD OD
Ingredients Quantity (g) Role of Ingredient
Pyroxasulfone (Purity: 98.0% w/w) 31 29.4 33.7 31 31 29.4 31.0 33.7 31 31 31 31 Active Ingredient
Cyhalofop-butyl (Purity: 97.5% w/w) 18.5 16.2 21.7 18.5 18.5 16.2 18.5 21.7 18.5 18.5 18.5 18.5 Active Ingredient
Penoxsulam
(Purity: 98.0% w/w) 5.5 3.8 7.7 5.5 5.5 3.8 5.5 7.7 5.5 5.5 5.5 5.5 Active Ingredient
Ethoxylated sorbitan ester ---- ---- ---- 3.2 ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Alkylnaphthalene sulfonate condensate 4.3 3.8 ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Sodium Polycarboxylate 2.4 ---- 3.5 ---- ---- ---- ---- ---- ---- ---- 0.8 ---- Dispersing agent
Acrylic copolymer ---- ---- ---- ---- 2.6 ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Anionic surfactant of Naphthalene sulphonic acid condensate ---- ---- ---- ---- 0.5 0.3 ---- ---- ---- ---- ---- ---- Dispersing agent
Lignosulfonate sodium salts sulfomethylated ---- 2.3 ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Nonionic methoxypropoxylated polyarylphenol ---- ---- ---- ---- ---- 1.8 ---- ---- ---- ---- ---- 3.2 Dispersing agent
Lignosulphonic acid, sodium salt ---- ---- 4.4 0.5 ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Low degree Sulfonated kraft lignin ---- ---- ---- ---- ---- ---- 0.5 ---- ---- ---- ---- ---- Wetting agent
Sodium polycarboxylate ---- ---- ---- 1.8 ---- ---- ---- ---- ---- ---- ---- ---- Wetting agent
Sodium dodecyl sulphate ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.5 ---- Wetting agent
Sodium Methyl Cocoyl Taurate 2.2 ---- 2.5 ---- ---- ---- ---- ---- ---- ---- ---- ---- Wetting agent
Sodium isopropyl naththanene sulphonate ---- ---- ---- ---- 0.5 ---- ---- ---- ---- ---- ---- ---- Wetting agent
Hydrophilic methoxypropoxylated polyarylphenol ---- 2.7 ---- ---- ---- 0.5 ---- ---- ---- ---- ---- 2.5 Wetting agent
Tristyrylphenol ethoxylated ---- ---- ---- ---- ---- ---- ---- 12 ---- ---- ---- ---- Emulsifying agent
Calcium dodecylbenzene sulphonate ---- ---- ---- ---- ---- ---- ---- ---- 12 ---- ---- ---- Emulsifying agent
Blend of Calcium alkyl benzene sulphonate and alkoxy alkyl ether ---- ---- ---- ---- ---- ---- ---- ---- ---- 12 ---- ---- Emulsifying agent
Tristrylphenol ethoxylate phosphate ester ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.8 Emulsifying agent
Alkyl benzene sulfonate, calcium salt ---- ---- ---- ---- ---- ---- 0.5 ---- ---- ---- ---- ---- Emulsifying agent
Sodium Polyacrelate ---- ---- ---- ---- ---- 2.8 ---- 1.0 0.5 ---- 1.3 ---- Thickner and Emulsion stabilizer
Synthetic polymer ---- ---- ---- ---- 2.5 ---- ---- ---- ---- ---- 0.4 ---- Thickner and
emulsion stabilizer
Polyvinylpyrrolidone ---- ---- ---- ---- ---- ---- 0.5 ---- ---- ---- ---- ---- Thickner and emulsion stabilizer
Low degree Sulfonated kraft lignin ---- ---- ---- ---- ---- ---- 0.3 ---- ---- ---- ---- ---- Stabilizer cum dispersing agent
Ricinoleic acid triglyceride ---- ---- ---- ---- ---- ---- ---- ---- ---- 2.5 ---- ---- Stabilizer
Sodium carbonate ---- ---- ---- ---- ---- ---- 0.1 ---- ---- ---- ---- ---- Buffering agent
Multiple nonionic tristyryphenol ---- ---- ---- ---- ---- ---- 2.5 ---- ---- ---- ---- ---- Emulsification and Dispersion
Solvesso 150 ---- ---- ---- ---- ---- 25 ---- ---- ---- ---- ---- ---- Solvent
Aromatic hydrocarbon ---- ---- ---- ---- ---- ---- ---- 21.4 ---- ---- ---- ---- Solvent
Heavy aeromatic naptha ---- ---- ---- ---- ---- ---- 20.0 ---- ---- ---- ---- ---- Solvent
Mixture of aromatic hydrocarbons ---- ---- ---- ---- ---- ---- ---- ---- ---- 20.5 ---- ---- Solvent
N-Methyl-2-pyrrolidone ---- ---- ---- ---- ---- ---- ---- ---- 29.3 10 ---- ---- Solvent
Mixture of aromatic hydrocarbons ---- ---- ---- ---- 25 ---- ---- ---- ---- ---- ---- ---- Solvent
Polydimethyl siloxane 0.5 0.3 ---- ---- ---- ---- 1.0 ---- ---- ---- 0.5 ---- Anti-foaming agent
Silicon Deformer ---- ---- 0.3 0.5 0.3 0.4 ---- ---- ---- ---- ---- ---- Anti-foaming agent
Polyvinyl pyrilidone ---- ---- ---- ---- 1.3 1.2 ---- ---- ---- ---- ---- ---- Binding agent
Precipitated silica ---- 1.3 ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- Anti-caking agent
Propane-1,2 Diol ---- ---- ---- ---- ---- 0.3 ---- ---- ---- ---- 3.5 ---- Anti-freezing agent/ Stabilizer
Propane- 1,2,3-triol ---- 2.5 ---- ---- 0.25 ---- 5.2 ---- ---- ---- ---- ---- Anti-freezing agent/ Stabilizer
Fatty acids, polycondensed 3.5 ---- 2.4 4.5 ---- ---- ---- 2.5 ---- ---- ---- ---- Anti-freezing agent/ Stabilizer
Propylene glycol ---- ---- ---- ---- ---- ---- ---- ---- 3.2 ---- ---- ---- Anti-freezing agent/ Stabilizer
Sodium carbonate 0.5 ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- Buffering agent
Ricinoleic acid triglyceride ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 35.85 Carrier agent
1,2-Benzisothiazoline-3-one ---- ---- ---- 0.15 0.8 0.1 0.1 ---- ---- ---- 0.15 0.15 Biocide/ Preservative
Bentonite clay ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.2 ---- Rheology modifier
Xanthan gum 0.15 0.17 0.18 ---- ---- ---- ---- ---- ---- ---- ---- ---- Rheology modifier
Polysaccharide ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 1.5 Rheology modifier
Disaccharide composed ---- ---- ---- 0.16 ---- ---- ---- ---- ---- ---- ---- ---- Thickening agent
Heteropolysaccharide ---- ---- ---- ---- ---- ---- 0.2 ---- ---- ---- ---- ---- Structuring agent
Soyamethyl ester ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 35.65 ---- Bio solvent
Aqua / Water 31.5 37.5 23.6 34.19 11.3 18.2 14.1 ---- ---- ---- ---- ---- Continues phase / Filler
Total 100g 100g 100g 100g 100g 100g 100g 100g 100g 100 g 100g 100g ----

Example 38 to 48: Formulation 4 - Pyroxasulfone + Topramezone + Ametryn

Example No. 38 39 40 41 42 43 44 45 46 47 48
Formulation Type WP WP WP WP WG WG WG WG SC SC SC
Ingredients Quantity (g) Role of Ingredient
Pyroxasulfone (Purity: 98.0% w/w) 4.2 3.7 4.7 4.2 4.2 3.7 4.7 4.2 4.2 4.7 4.2 Active Ingredient
Topramezone
(Purity: 96.0% w/w) 1.1 0.6 1.5 1.1 1.1 0.6 1.5 1.1 1.1 1.5 1.1 Active Ingredient
Ametryn
(Purity: 97.0% w/w) 65 62 68.5 65.0 65 62 68.5 65.0 65 68.5 65.0 Active Ingredient
Acrylic polymer ---- ---- ---- ---- ---- ---- ---- ---- ---- 3.0 4.0 Surfactant
Alkylnaphthalene sulfonate condensate 4.85 3.8 ---- ---- ---- 10.0 ---- ---- ---- ---- ---- Dispersing agent
Sodium Polycarboxylate 1.2 ---- 3.5 5.0 ---- ---- ---- ---- ---- 1.7 ---- Dispersing agent
Acrilyc copolymer ---- ---- ---- 5.0 2.9 ---- 5.3 ---- 3.2 ---- ---- Dispersing agent
Lignosulphonic acid, sodium salt ---- ---- 4.4 ---- 3.3 ---- ---- ---- ---- 0.5 ---- Dispersing agent
Lignosulfonate sodium salts sulfomethylated ---- 2.3 ---- ---- ---- ---- ---- ---- ---- ---- ---- Dispersing agent
Methyl naphthalin sulphonate sodium salt ---- ---- ---- ---- ---- ---- ---- 5.0 ---- ---- ---- Dispersing agent
Sodium Lignosulphonate ---- ---- ---- ---- ---- ---- ---- 5.0 ---- ---- ---- Dispersing agent
Tristyrylphenol Ethoxylate Phosphate Ester ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 3.0 Emulsification and Dispersion
Sodium dodecyl sulphate 3.75 ---- ---- ---- ---- 4.0 ---- ---- ---- 1.5 ---- Wetting agent
Sodium Methyl Cocoyl Taurate ---- ---- 2.5 3.0 ---- ---- ---- ---- 1.8 ---- ---- Wetting agent
sodium isopropyl naththanene sulphonate ---- ---- ---- ---- 2.4 ---- 3.4 3.0 ---- ---- ---- Wetting agent
Hydrophilic ethpropoxylated polyarylphenol ---- 2.7 ---- ---- ---- ---- ---- ---- ---- ---- ---- Wetting agent
Calcium alkylaryl sulphonate ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 2.0 Wetting agent
Polydimethyl siloxane ---- ---- ---- ---- 0.5 1.0 0.5 0.5 0.5 0.5 0.5 Antifoaming agent
Deformer ---- ---- ---- 0.5 ---- ---- ---- ---- ---- ---- ---- Antifoaming agent
Polyvinyl pyrilidone ---- ---- ---- ---- ---- 1.0 ---- ---- ---- ---- ---- Binding agent
Polymeric carbohydrate ---- ---- ---- ---- ---- ---- 0.4 5.0 ---- ---- ---- Binding agent
Sio2 anhydrous ---- ---- ---- ---- ---- ---- ---- 1.0 ---- ---- ---- Thickening agent
Polysaccharide ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 0.2 Thickening agent
Precipitated silica ---- 1.3 ---- ---- 1.1 ---- ---- ---- ---- ---- ---- Anti-caking agent
Propane-1,2 Diol ---- ---- ---- ---- ---- ---- ---- ---- ---- 3.5 4.0 Anti-freezing agent/ Stabilizer
Propylene glycol ---- ---- ---- ---- ---- ---- ---- ---- 4.8 ---- ---- Anti-freezing agent/ Stabilizer
Soda ash ---- ---- ---- ---- ---- ---- 0.2 ---- ---- ---- ---- Buffering agent
1,2-Benzisothiazoline-3-one ---- ---- ---- ---- ---- ---- ---- ---- 0.25 0.15 0.1 Biocide/ Preservative
Xanthan gum ---- ---- ---- ---- ---- ---- ---- ---- 0.18 ---- ---- Rheology modifier
Fume silica ---- ---- ---- ---- ---- 3 ---- ---- ---- ---- ---- Filler
Kaolin 19.9 ---- ---- ---- ---- 14.7 ---- ---- ---- ---- ---- Filler
Chinaclay ---- ---- ---- ---- 19.5 ---- 15.5 ---- ---- ---- ---- Filler
Kaolinite ---- ---- ---- 16.2 ---- ---- ---- ---- ---- ---- ---- Inert
Hydrated magnasium silicate ---- ---- ---- ---- ---- ---- ---- 10.2 ---- ---- ---- Inert
Dioctahedral phyllosilicate clay ---- 23.6 14.9 ---- ---- ---- ---- ---- ---- ---- ---- Carrier agent
Aqua / Water ---- ---- ---- ---- ---- ---- ---- ---- 18.97 14.45 15.9 Continues phase / Filler
Total 100g 100g 100g 100g 100g 100g 100g 100g 100g 100g 100g ----

Example 49: Process for Preparation of Suspension Concentrate (SC)
Step 1 Charge DM water in clean and dry reactor fitted with stirrer
Step 2 Add all excipients one by one under stirring
Step 3 Mix for 30 min. under ambient temperature to complete homogeneity
Step 4 Add all active ingredients one by one slowly under stirring
Step 5 Mix for 30 min. to complete homogeneity of above slurry
Step 6 Pass through Beadmill the above homogenized slurry to achieve particle size between 0.5 micron to 50 micron of SC formulation

The requisite quantities of actives and excipients used to prepare SC formulation mentioned in the above process can be taken from any of Example nos. 1, 2, 3, 20, 21, 22, 26, 27, 28, 29, 46, 47 and 48.

Example 50: Process for Preparation of Suspo-emulsion (SE)
Step 1 Charge active ingredient (Propaquizafop / Cyhalofop / Topramezone) in solvent and dissolve completely in reactor-1
Step 2 Add thickener and emulsion stabilizer and mix thru high rpm stirring
Step 3 Stir for 30 min. at more than 800 rpm to get EW form
Step 4 Charge water in reactor-2 fitted with stirrer
Step 5 Add all the remaining excipients one by one under stirring in reactor-2
Step 6 Mix for 30 min. under ambient temperature to obtain complete homogenize slurry
Step 7 Add remaining two active ingredient (Pyroxasulfone and Tembotrione / Mesotrione / Halosulfuron / Ametryn / Penoxsulam) one by one slowly under stirring
Step 8 Mix for 30 min. to obtain complete homogeneity of above slurry
Step 9 Bead mill the slurry to achieve between 0.5 to 50 micron particle size
Step 10 After achieving particle size, this slurry became SC form
Step 11 Transfer reactor-2, SC form obtain in Step 10 into reactor-1, EW form of Step 3
Step 12 Homogenize mixture of Step 11 completely and this final mixture became SE form
EW: Emulsion-in-water; SC: Suspension concentrate; SE: Suspo-emulsion

The requisite quantities of actives and excipients used to prepare SE formulation mentioned in the above process can be taken from any of Example nos. 11, 23, 24, 25, 30, 31 and 32.

Example 51: Process for Preparation of Water Dispersible Granule (WDG/WG)
Step 1 Charge all excipients and active ingredients in pre-blender
Step 2 Mix for 30 min. under ambient temperature to complete homogeneity
Step 3 Grind the above pre-blending material through air jet-mill until to achieve particle size between 0.5 to 50 microns
Step 4 Post blending for 30 minutes to homogenize milled premix
Step 5 Charge milled premix in dough maker to prepare dough
Step 6 Spray DM water under stirring as required quantity to attain proper dough
Step 7 Charge dough material in extruder
Step 8 Collect granules on conveyor belt and charge granules in dryer above 50°C temperature to obtain WDG formulation

The requisite quantities of actives and excipients used to prepare WDG/WG formulation mentioned in the above process can be taken from any of Example nos. 16, 17, 18, 19, 42, 43, 44 and 45.

Example 52: Process for Preparation of Wettable Powder (WP)
Step 1 Charge all excipients and active ingredients in pre-blender
Step 2 Mix for 30 min. under ambient temperature to complete homogeneity
Step 3 Grind the above pre-blending material through air jet-mill until to achieve particle size between 0.5 to 50 microns
Step 4 Post blending for 30 minutes to homogenize milled premix to make WP formulation

The requisite quantities of actives and excipients used to prepare WP formulation mentioned in the above process can be taken from any of Example nos. 12, 13, 14, 15, 38, 39, 40 and 41.

Example 53: Process for Preparation of Emulsion Concentrate (EC)
Step 1 Charge solvent in reactor fitted with stirrer
Step 2 Add all three active ingredients one by one under stirring and dissolve completely
Step 3 Add stabilizer and emulsifier
Step 4 Homogenize the mixture of Step 3 completely to obtain EC formulation

The requisite quantities of actives and excipients used to prepare EC formulation mentioned in the above process can be taken from any of Example nos. 7, 8, 9, 10, 33, 34 and 35.

Example 54: Process for Preparation of Oil Dispersion (OD)
Step 1 Charge carrier agent in reactor fitted with high-speed stirrer
Step 2 Charge wetting agent, dispersing agent, emulsifier and preservative one by one
Step 3 Add all three active ingredients one by one slowly under stirring
Step 4 Mix thru high speed stirring for 30 min. to complete homogeneity
Step 5 Add rheology modifier and obtain homogenize mass as OD formulation

The requisite quantities of actives and excipients used to prepare OD formulation mentioned in the above process can be taken from any of Example nos. 4, 5, 6, 36 and 37.

Bio-efficacy Studies:

Example 55: Bio-efficacy and Phytotoxicity to Sugarcane
The field experiment was conducted on Sugarcane crop and experimental details as below:
Crop Sugarcane
Experimental design Randomized block design (R.B.D)
Replications Three
No. of Treatments 16
Plot size 52 sq. mt.
Application Time 2 to 4 leaf stage of weeds
Observations At 7 and 15 DAA (Days after Application) for Phytotoxicity and
7 and 15 DAA (Days after Application) for Bio-efficacy against mixed weed flora
Spray Volume 500 liter water per hectare
Application Equipment Manually operated knap sack sprayer fitted with flat fan nozzle

Experimental Methodology:
Sugarcane crop was raised as per the standard agronomic practices in the field to conduct a trial to assess phytotoxicity of different inventive synergistic mixtures.

The trial was laid out in Randomized Block Design (R.B.D.) with sixteen treatments including untreated check (UTC), replicated three times. For each treatment plot size of 52 sq. mt. was maintained. The application of different treatments with prescribed doses was done with manually operated knapsack sprayer fitted with flat fan nozzle. The spray volume was used at 500 l/h for spraying. The Untreated check plot was sprayed with water alone. Observations on Phytotoxicity viz., yellowing, stunting, epinasty and hyponasty was recorded at 10 and 20 days after spraying, by adopting 0-10 rating scale as below:

Scale Rate Phytotoxicity Percentage
1 1-10%
2 11-20%
3 21-30%
4 31-40%
5 41-50%
6 51-60%
7 61-70%
8 71-80%
9 81-90%
10 91-100%

Percent Phytotoxicity was calculated by following formula:
Sum of all scores
% Phytotoxicity = ------------------------------------------------------------- X 100
Number of samples x highest rating scale

Species wise weed count recorded at 7 and 15 DAA (Days After Application) by using 0.25m2 quadrant treatment wise in minimum 4 places randomly selected in the plot per replication. The average of each variable was used together with the sum of all the variables per plot to calculate the percentage of control.

Mean weed count in untreated plot – Mean weed control in treated
% Weed Control = 1 - (----------------------------------------------------------------------------------- ) X 100
Mean weed count in untreated plot

The % weeds control data used in Colby’s formula to calculate the synergism between three herbicide.

Table 1: Treatment details in Sugarcane Crop
Treat-ment Formulation Active ingredient Dosage
(ml or gm per hectare)
T1 Pyroxasulfone 4.2% + Topramezone 1.1% + Ametryn 65% WG 2500
T2 Pyroxasulfone 23% + Tembotrione 22% + Halosulfuron methyl 10% SE 500
T3 Pyroxasulfone 85% WG + Topramezone 33.6% SC + Ametryn 80% WG 150 + 100 + 2500
T4 Pyroxasulfone 85% WG + Tembotrione 34.4% SC + Halosulfuron methyl 75% WG 150 + 286 + 90
T5 Pyroxasulfone 85% WG + Topramezone 33.6% SC 150 + 100
T6 Pyroxasulfone 85% WG + Tembotrione 34.4% SC 150 + 286
T7 Topramezone 33.6% SC + Ametryn 80% WG 100 + 2500
T8 Tembotrione 34.4% SC + Halosulfuron methyl 75% WG 286 + 90
T9 Pyroxasulfone 85% WG + Ametryn 80% WG 150 + 2500
T10 Pyroxasulfone 85% WG + Halosulfuron methyl 75% WG 150 + 90
T11 Pyroxasulfone 85% WG 150
T12 Topramezone 33.6% SC 100
T13 Ametryn 80% WG 2500
T14 Tembotrione 34.4% SC 286
T15 Halosulfuron methyl 75% WG 90
T16 Untreated Control N.A
WG: Water dispersible granules; SC: Suspension concentrate
T1 to T2: Present formulations
T3 to T10: Tank mix of marketed products
T11 to T15: Market available products

Table 2: Phytotoxicity on Sugarcane crop
Treatment Yellowing (%) Stunting (%) Epinasty (%) Hyponasty (%)
7 DAA 15 DAA 7 DAA 15 DAA 7 DAA 15 DAA 7 DAA 15 DAA
T1 0 0 0 0 0 0 0 0
T2 0 0 0 0 0 0 0 0
T3 0 0 0 0 0 0 0 0
T4 0 0 0 0 0 0 0 0
T5 0 0 0 0 0 0 0 0
T6 0 0 0 0 0 0 0 0
T7 0 0 0 0 0 0 0 0
T8 0 0 0 0 0 0 0 0
T9 0 0 0 0 0 0 0 0
T10 0 0 0 0 0 0 0 0
T11 0 0 0 0 0 0 0 0
T12 0 0 0 0 0 0 0 0
T13 0 0 0 0 0 0 0 0
T14 0 0 0 0 0 0 0 0
T15 0 0 0 0 0 0 0 0
T16 0 0 0 0 0 0 0 0
DAA - Days after Application

The results of the field trial on crop phytotoxicity presented in Table 2 indicates that the present formulations did not cause any significant damage to crop and crop vigor and growth. Overall all tested combinations were found safe to the Sugarcane crop.

Table 3: Bio-efficacy against all weeds in Sugarcane crop
Treatment Weed control at 7 DAA (%) Weed control at 15 DAA (%) Colby ratio
(Obs./Exp.)
Expected Observed Expected Observed 7 DAA 15 DAA
T1 87.8 95.9 81.0 90.7 1.09 1.12
T2 84.8 94.5 74.7 88.2 1.11 1.18
T3 87.8 93.2 81.0 85.2 1.06 1.05
T4 84.8 91.6 74.7 81.0 1.08 1.08
T5 81.9 80.4 76.7 71.3 0.98 0.93
T6 80.1 77.5 76.3 66.9 0.97 0.88
T7 77.9 72.3 71.6 64.2 0.93 0.90
T8 73.6 70.3 66.6 62.1 0.95 0.93
T9 68.5 59.6 64.2 53.5 0.87 0.83
T10 65.8 58.7 58.6 51.8 0.89 0.88
T11 - 49.2 - 45.8 - -
T12 - 64.3 - 57.1 - -
T13 - 38.0 - 33.9 - -
T14 - 60.9 - 56.2 - -
T15 - 32.6 - 23.7 - -
T16 - NA - NA - -

Weed flora of trial plot: Grassy weeds (Echinochloa colonum, Cynodon dactylon), Broad leaf weeds (Trianthema spp., Amaranthus spp., Digera spp.), Sedges (Cyperus rotundus).

The field trials results presented in Table 3 indicate that present formulations (T1 and T2) comprising combination of Pyroxasulfone + Topramezone + Ametryn (T1) and Pyroxasulfone + Tembotrione + Halosulfuron methyl (T2) exhibits synergistic effect as well as longer duration of weed control over tank mix of marketed products (T3 to T10) and solo formulations (market available products) (T11 to T15).

Example 56: Bio-efficacy and Phytotoxicity to Paddy
The field experiment was conducted on paddy crop and experimental details as below:
Crop Paddy
Experimental design Randomized block design (R.B.D)
Replications Three
No. of Treatments 16
Plot size 42 sq. mt.
Application Time 2 to 4 leaf stage of weeds
Observations At 7 and 15 DAA (Days after Application) for Phytotoxicity and
7 and 15 DAA (Days after Application) for Bio-efficacy against mixed weed flora
Spray Volume 500 liter water per hectare
Application Equipment Manually operated knap sack sprayer fitted with flat fan nozzle

Experimental Methodology:
Paddy crop was raised as per the standard agronomic practices in the field to conduct a trial to assess phytotoxicity of different inventive synergistic mixtures.

The trial was laid out in Randomized Block Design (RBD) with sixteen treatments including untreated check (UTC), replicated three times. For each treatment plot size of 42 sq. mt was maintained. The application of different treatments with prescribed doses was done with manually operated knapsack sprayer fitted with flat fan nozzle. The spray volume was used at 500 l/h for spraying. The Untreated check plot was sprayed with water alone.

Table 4: Treatment details in Paddy
Treatment Formulation Active ingredient Dosage
(ml or gm per hectare)
T1 Pyroxasulfone 31% + Cyhalofop-butyl 18.5% + Penoxsulam 5.5% SC 375
T2 Pyroxasulfone 21% + Mesotrione 35% + Propaquizafop 8% OD 550
T3 Pyroxasulfone 85% WG + Cyhalofop-butyl 10% EC + Penoxsulam 2.67% OD 150 + 800 + 1000
T4 Pyroxasulfone 85% WG + Mesotrione 40% SC + Propaquizafop 10% EC 150 + 530 + 750

T5 Pyroxasulfone 85% WG + Cyhalofop-butyl 10% EC 150 + 800
T6 Pyroxasulfone 85% WG + Mesotrione 40% SC 150 + 530
T7 Cyhalofop-butyl 10% EC + Penoxsulam 2.67% OD 800 + 1000
T8 Mesotrione 40% SC + Propaquizafop 10% EC 530 + 750
T9 Pyroxasulfone 85% WG + Penoxsulam 2.67% OD 150 + 1000
T10 Pyroxasulfone 85% WG + Propaquizafop 10% EC 150 + 750
T11 Pyroxasulfone 85% WG 150
T12 Cyhalofop butyl 10% EC 800
T13 Penoxsulam 2.67% OD 1000
T14 Mesotrione 40% SC 530
T15 Propaquizafop 10% EC 750
T16 Untreated Control N.A
SC: Suspension concentrate; OD: Oil dispersion
T1 to T2: Present formulations
T3 to T10: Tank mix of marketed products
T11 to T15: Market available products

Table 5: Phytotoxicity on Paddy crop
Treatment Yellowing (%) Stunting (%) Epinasty (%) Hyponasty (%)
7 DAA 15 DAA 7 DAA 15 DAA 7 DAA 15 DAA 7 DAA 15 DAA
T1 0 0 0 0 0 0 0 0
T2 0 0 0 0 0 0 0 0
T3 0 0 0 0 0 0 0 0
T4 0 0 0 0 0 0 0 0
T5 0 0 0 0 0 0 0 0
T6 0 0 0 0 0 0 0 0
T7 0 0 0 0 0 0 0 0
T8 0 0 0 0 0 0 0 0
T9 0 0 0 0 0 0 0 0
T10 0 0 0 0 0 0 0 0
T11 0 0 0 0 0 0 0 0
T12 0 0 0 0 0 0 0 0
T13 0 0 0 0 0 0 0 0
T14 0 0 0 0 0 0 0 0
T15 0 0 0 0 0 0 0 0
T16 0 0 0 0 0 0 0 0
DAA - Days after Application

The results of the field trial on crop phytotoxicity presented in Table 5 indicates that the present formulations did not cause any significant damage to crop and crop strength and growth. Overall all tested combinations were found safe to the Paddy crop.

Table 6: Bio-efficacy against all weeds in Paddy crop
Treatment Weed control at 7 DAA (%) Weed control at 15 DAA (%) Colby ratio (Obs./Exp.)
Expected Observed Expected Observed 7 DAA 15 DAA
T1 83.4 96.3 75.8 90.1 1.15 1.19
T2 82.7 93.1 75.3 86.4 1.13 1.15
T3 83.4 92.4 75.8 85.9 1.11 1.13
T4 82.7 89.6 75.3 82.3 1.08 1.09
T5 67.0 64.2 60.6 55.1 0.96 0.91
T6 76.7 72.9 69.4 63.1 0.95 0.91
T7 71.0 68.3 62.9 60.6 0.96 0.96
T8 71.8 69.6 64.2 59.1 0.97 0.92
T9 75.5 62.4 69.2 56.8 0.83 0.82
T10 66.4 60.7 61.7 53.9 0.91 0.87
T11 - 47.3 - 42.8 - -
T12 - 37.4 - 31.1 - -
T13 - 53.6 - 46.1 - -
T14 - 55.8 - 46.5 - -
T15 - 36.3 - 33.1 - -
T16 - NA - NA - -

Weed flora of trial plot: Grassy weeds (Echinochloa colonum, Digitaria spp., Cynodon dactylon), Broad leaf weeds (Trianthema spp., Amaranthus spp.), Sedges (Cyperus rotundus).

The field trials results presented in Table 6 indicate that present formulations (T1 and T2) comprising combination of Pyroxasulfone + Cyhalofop-butyl + Penoxsulam (T1) and Pyroxasulfone + Mesotrione + Propaquizafop (T2) exhibits synergistic effect as well as longer duration of weed control over tank mix of marketed products (T3 to T10) and solo formulations (market available products) (T11 to T15).

Advantages of present invention:
• The present synergistic herbicidal composition having broad spectrum activity and overcome herbicidal resistance.
• The present synergistic herbicidal composition shows effective treatment and prevention against growth or germination of weeds.
• The present synergistic herbicidal composition achieves improved biological activity by enhancing overall control of weeds over a shorter period of time.
• The present synergistic herbicidal composition shows enhanced herbicide activity in comparison with herbicide activity of solo ingredient formulations and known/marketed formulations.
• The present synergistic herbicidal composition comprises effective combination of more than one agrochemical that allows the application of the said agrochemical in a much lower dosage, which results in a less dosage treatment for the crops.
• The present synergistic herbicidal composition is non-phytotoxic to crop/plants.
,CLAIMS:We Claim,

1. A synergistic herbicidal formulation comprising;
(A) Pyroxasulfone;
(B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione;
(C) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam;
along with one or more agrochemically acceptable adjuvants/excipients.

2. The synergistic herbicidal formulation as claimed in claim 1; wherein Pyroxasulfone is present in an amount of 2 to 45% by weight of total formulation.

3. The synergistic herbicidal formulation as claimed in claim 1; wherein herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione is present in an amount of 0.5 to 40% by weight of total formulation.

4. The synergistic herbicidal formulation as claimed in claim 1; wherein herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam is present in an amount of 3 to 70% by weight of total formulation.

5. The synergistic herbicidal formulation as claimed in claim 1; wherein agrochemically acceptable adjuvants/excipients is present in an amount of 0.1 to 40% by weight of total formulation.

6. The synergistic herbicidal formulation as claimed in claim 1; wherein agrochemically acceptable adjuvants/excipients is selected from dispersing agents/dispersants, wetting agents, emulsifying agents/emulsifiers, stabilizing agents/stabilizers, thickening agents/thickeners, solubilizing agents/solubilizers, binding agents/binders, buffering agents, structuring agents, thickner and emulsion stabilizers, emulsification and dispersion, stabilizer cum dispersing agents, surfactants, anti-freezing agents, anti-foaming agents, anti-caking agents, biocides/preservatives, rheology modifiers, solvents, bio-solvents, carrier agents/carriers, inerts and fillers/continues phase thereof.

7. The synergistic herbicidal formulation as claimed in claim 6; wherein dispersing agents/dispersants selected from alkylnaphthalene sulfonate condensate, dodycylbenzenesulfonic acid sodium salt, octyl phenol ethoxylate, nonionic tristyryphenol, sodium lignosulfonate, sodium lignosulfonate ethoxylated, polyalkoxylated butyl ether, low degree sulfonated kraft lignin, nonionic ethopropoxylated polyarylphenol, styrene acrylic polymer, acrylic copolymer, ethoxylated sorbitan ester, lignosulphonic acid sodium salt, calcium salt of alkyl benzin sulphonate, tristyrylphenol ethoxylate phosphate ester, sodium polycarboxylate, methyl naphthalin sulphonate sodium salt, acrylate copolymer, anionic surfactant of naphthalene sulphonic acid condensate, lignosulfonate sodium salts sulfomethylated and sodium lignosulphonate; present in an amount of 0.1 to 12% of the total weight of the formulation.

8. The synergistic herbicidal formulation as claimed in claim 6; wherein wetting agents selected from lauryl alchohol condensate, mixture of mineral oils and alkyl aryl ether, low degree sulfonated kraft lignin, hydrophilic ethpropoxylated polyarylphenol, nonionic block copolymer, sodium polycarboxylate, calcium alkylaryl sulphonate, sodium dodecyl sulphate, sodium methyl cocoyl taurate, sodium isopropyl naththanene sulphonate, lauryl alcohol condensate, mixture of mineral oils and alkyl aryl ether, low degree sulfonated kraft lignin and sodium polycarboxylate; present in an amount of 0.2 to 5% of the total weight of the formulation.

9. The synergistic herbicidal formulation as claimed in claim 6; wherein emulsifying agents/emulsifiers selected from tristyrylphenol ethoxylated, calcium dodecylbenzene sulphonate, blend of calcium alkyl benzene sulphonate and alkoxy alkyl ether, tristrylphenol ethoxylate phosphate ester, fatty acids polycondensed, alkyl benzene sulfonate calcium salt, dodycylbenzenesulfonic acid sodium salt, octyl phenol ethoxylate, nonionic tristyryphenol and linear calcium dodecylbenzine sulphonate; present in an amount of 0.1 to 15% of the total weight of the formulation

10. The synergistic herbicidal formulation as claimed in claim 6; wherein stabilizing agents/stabilizers selected from Propane-1,2 Diol, Propane- 1,2,3-triol, propylene glycol, fatty acids polycondensed, sodium polyacrelate, polyacrylate copolymer, synthetic polymer, polyvinylpyrrolidone, 1,2-Dihydroxyethane and ricinoleic acid triglyceride; present in an amount of 0.1 to 6% of the total weight of the formulation.

11. The synergistic herbicidal formulation as claimed in claim 6; wherein thickening agents/thickeners selected from sodium polyacrylate, disaccharide composed, polysaccharide and SiO2 anhydrous; present in an amount of 0.1 to 1% of the total weight of the formulation

12. The synergistic herbicidal formulation as claimed in claim 6; wherein solubilizing agents/solubilizers selected from benzyl acetate, Solvesso 200, polyacrylate copolymer; present in an amount of 1 to 12 % of the total weight of the formulation.

13. The synergistic herbicidal formulation as claimed in claim 6; wherein binding agents/binders selected from polymeric carbohydrate, polyvinylpyrrolidone and polyvinyl alcohol; present in an amount of 0.1 to 1.5% of the total weight of the formulation.

14. The synergistic herbicidal formulation as claimed in claim 6; wherein buffering agents selected from soda ash, sodium carbonate ammonia, magnesium carbonate and acetic acid; present in an amount of 0.1 to 1% of the total weight of the formulation.

15. The synergistic herbicidal formulation as claimed in claim 6; wherein structuring agents selected from heteropolysaccharide and xanthan gum; present in an amount of 0.10 to 0.25% of the total weight of the formulation.

16. The synergistic herbicidal formulation as claimed in claim 6; wherein thickener and emulsion stabilizers selected from sodium polyacrylate, synthetic polymer and polyvinylpyrrolidone; present in an amount of 0.1 to 3% of the total weight of the formulation.

17. The synergistic herbicidal formulation as claimed in claim 6; wherein emulsification and dispersion selected from dodecylbenzene sulfonic acid sodium salt, calcium salt of alkyl benzene sulphonate, octyl phenol ethoxylate, multiple nonionic tristyryphenol and tristyrylphenol ethoxylate phosphate ester; present in an amount of 1 to 4% of the total weight of the formulation.

18. The synergistic herbicidal formulation as claimed in claim 6; wherein stabilizer cum dispersing agents selected from sodium lignosulfonate ethoxylated, poly alkoxylated butyl ether and low degree sulfonated kraft lignin; present in an amount of 0.1 to 2% of the total weight of the formulation.

19. The synergistic herbicidal formulation as claimed in claim 6; wherein surfactants selected from acrylic polymer, C12-15 ethoxylated alcohols and acrylic polymer; present in an amount of 0.1 to 5% of the total weight of the formulation.

20. The synergistic herbicidal formulation as claimed in claim 6; wherein anti-freezing agents selected from ricinoleic acid triglyceride, propane-1,2 diol, propane-1,2,3-triol, 1,2-dihydroxyethane, fatty acids polycondensed and propylene glycol; present in an amount of 0.1 to 6% of the total weight of the formulation.

21. The synergistic herbicidal formulation as claimed in claim 6; wherein anti-foaming agents selected from polydimethyl siloxane, deformer, silicon deformer and polydimethyl siloxane; present in an amount of 0.1 to 2% of the total weight of the formulation.

22. The synergistic herbicidal formulation as claimed in claim 6; wherein anti-caking agents selected from precipitated silica, silicon dioxide, calcium silicate, magnesium stearate, sodium aluminosilicate, potassium aluminium silicate, tricalcium phosphate, sodium ferrocyanide, calcium carbonate, diatomaceous earth and sodium bicarbonate; present in an amount of 0.2 to 1.5% of the total weight of the formulation.

23. The synergistic herbicidal formulation as claimed in claim 6; wherein biocides/preservatives selected from 1,2-benzisothiazolin-3-one; Proprietary mixture of 1,2 benziso thiazolin- 3-one, sodium hydroxide and dipropylene glycol in aqueous media; present in an amount of 0.1 to 0.8% of the total weight of the formulation.

24. The synergistic herbicidal formulation as claimed in claim 6; wherein rheology modifiers selected from bentonite clay, xanthan gum, polyvinyl alcohol and polysaccharide; present in an amount of 0.1 to 2% of the total weight of the formulation.

25. The synergistic herbicidal formulation as claimed in claim 6; wherein solvents selected from aromatic hydrocarbon, heavy aromatic naphtha, N-Methyl-2-pyrrolidone, mixture of aromatic hydrocarbons (Solvent C-9), Solvesso 200, Solvesso 150, soya methyl ester, benzyl acetate and heavy aromatic naphtha; present in an amount of 5 to 30% of the total weight of the formulation.

26. The synergistic herbicidal formulation as claimed in claim 6; wherein bio-solvents selected from soya methyl ester, ethanol, isopropyl ester, poly-p-phynele sulphide, and ethyl lactate; present in an amount of 30 to 40% of the total weight of the formulation.

27. The synergistic herbicidal formulation as claimed in claim 6; wherein carrier agents/carriers selected from ricinoleic acid triglyceride, dioctahedral phyllosilicate clay; present in an amount of 0.20 to 40% of the total weight of the formulation.

28. The synergistic herbicidal formulation as claimed in claim 6; wherein inerts selected from kaolinite, hydrated magnasium silicate, talc, chalk, quartz, calcite and talcum; present in an amount of 5 to 20% of the total weight of the formulation.

29. The synergistic herbicidal formulation as claimed in claim 6; wherein fillers/continues phase selected from aqua/water, fume silica, kaolin and china clay; present in an amount of 1 to 40% of the total weight of the formulation.

30. The synergistic herbicidal formulation as claimed in claims 1 to 5; wherein synergistic herbicidal formulation is formulated into formulation types selected from Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspoemulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WDG/WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE) and a mixed formulation of CS and EW (ZW).

31. The synergistic herbicidal formulation as claimed in claims 1 and 30; wherein synergistic herbicidal Suspension Concentrate (SC) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(g) buffering agent in an amount of 0.1 to 1% (w/w);
(h) anti-freezing agent in an amount of (w/w);
(i) anti-caking agent in an amount of 0.2 to 1.5% (w/w);
(j) thickening agent in an amount of 0.1 to 1% (w/w);
(k) surfactant in an amount of 0.1 to 5% (w/w);
(l) biocide/preservative in an amount of 0.1 to 0.8% (w/w);
(m) rheology modifier in an amount of 0.1 to 2% (w/w);
(n) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

32. The synergistic herbicidal formulation as claimed in as claimed in claims 1 and 30; wherein synergistic herbicidal Suspoemulsion (SE) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) emulsifying agent in an amount of 0.1 to 15% (w/w);
(g) binding agent in an amount of 0.1 to 1.5% (w/w);
(h) buffering agent in an amount of 0.1 to 1% (w/w);
(i) thickening agent in an amount of 0.1 to 1% (w/w);
(j) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(k) anti-caking agent in an amount of 0.2 to 1.5% (w/w);
(l) anti-freezing agent in an amount of 0.1 to 6% (w/w);
(m) structuring agent in an amount of 0.10 to 0.25% (w/w);
(n) thickener and emulsion stabilizer in an amount of 0.1 to 3% (w/w);
(o) emulsification and dispersion in an amount of 1 to 4% (w/w);
(p) stabilizer cum dispersing agent in an amount of 0.1 to 2% (w/w);
(q) biocide/preservative in an amount of 0.1 to 0.8% (w/w);
(r) rheology modifier in an amount of 0.1 to 2% (w/w);
(s) solvent in an amount of 5 to 30% (w/w);
(t) carrier agent in an amount of 0.20 to 40% (w/w);
(u) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

33. The synergistic herbicidal formulation as claimed in claims 1 and 30; wherein synergistic herbicidal Water dispersible granule (WDG/WG) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) buffering agent in an amount of 0.1 to 1% (w/w);
(g) binding agent in an amount of 0.1 to 1.5% (w/w);
(h) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(i) anti-caking agent in an amount of 0.2 to 1.5% (w/w);
(j) carrier agent in an amount of 0.20 to 40% (w/w);
(k) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

34. The synergistic herbicidal formulation as claimed in claims 1 and 30; wherein synergistic herbicidal Wettable Powder (WP) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(g) anti-caking agent in an amount of 0.2 to 1.5% (w/w);
(h) carrier agent in an amount of 0.20 to 40% (w/w);
(i) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

35. The synergistic herbicidal formulation as claimed in claims 1 and 30; wherein synergistic herbicidal Emulsifiable concentrate (EC) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) binding agent in an amount of 0.1 to 1.5% (w/w);
(g) emulsifying agent in an amount of 0.1 to 15% (w/w);
(h) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(i) anti-freezing agent in an amount of 0.1 to 6% (w/w);
(j) thickening agent in an amount of 0.1 to 1% (w/w);
(k) surfactant in an amount of 0.1 to 5% (w/w);
(l) stabilizer in an amount of 0.1 to 6% (w/w);
(m) thickener and emulsion stabilizer in an amount of 0.1 to 3% (w/w);
(n) biocide/preservative in an amount of 0.1 to 0.8% (w/w);
(o) rheology modifier in an amount of 0.1 to 2% (w/w);
(p) solvent in an amount of 5 to 30% (w/w);
(q) filler in an amount of 1 to 40% (w/w) of the total weight of the formulation.

36. The synergistic herbicidal formulation as claimed in claims 1 and 30; wherein synergistic herbicidal Oil dispersion (OD) formulation comprising;
(a) Pyroxasulfone in an amount of 2 to 45% (w/w);
(b) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40% (w/w);
(c) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% (w/w);
(d) dispersing agent in an amount of 0.1 to 12% (w/w);
(e) wetting agent in an amount of 0.2 to 5% (w/w);
(f) emulsifying agent in an amount of 0.1 to 15% (w/w);
(g) binding agent in an amount of 0.1 to 1.5% (w/w);
(h) anti-foaming agent in an amount of 0.1 to 2% (w/w);
(i) anti-freezing agent/ stabilizer in an amount of 0.1 to 6% (w/w);
(j) thickener and emulsion stabilizer in an amount of 0.1 to 3% (w/w);
(k) surfactant in an amount of 0.1 to 5% (w/w);
(l) biocide/preservative in an amount of 0.1 to 0.8% (w/w);
(m) rheology modifier in an amount of 0.1 to 2% (w/w);
(n) solvent in an amount of 5 to 30% (w/w);
(o) carrier agent in an amount of 0.20 to 40% (w/w);
(p) bio-solvent in an amount of 30 to 40% (w/w) of the total weight of the formulation.

37. A process for preparation of suspension concentrate (SC) formulation as claimed in claim 31 comprises the steps of;
(a) Mixing DM water with dispersing agent, wetting agent, anti-foaming agent, buffering agent, anti-freezing agent, anti-caking agent, thickening agent, surfactant, biocide/preservative, rheology modifier and filler one by one under stirring followed by mixing for 30 minutes under ambient temperature to completely homogenized;
(b) adding all active ingredients one by one slowly in step (a) under stirring and mixing for 30 minutes to completely homogenized; and
(c) passing the homogenized slurry of step (b) through beadmill to achieve desired particle size of SC formulation.

38. A process for preparation of suspo-emulsion (SE) formulation as claimed in claim 32 comprises the steps of;
(a) dissolving Propaquizafop / Cyhalofop-butyl / Topramezone in solvent and adding thickener and emulsion stabilizer followed by mixing through more than 800 rpm for 30 minutes to obtain EW form;
(b) mixing water with dispersing agent, wetting agent emulsifying agent binding agent buffering agent thickening agent anti-foaming agent anti-caking agent anti-freezing agent structuring agent, thickener and emulsion stabilizer, emulsification and dispersion, stabilizer cum dispersing agent biocide/preservative, rheology modifier, solvent, carrier agent and filler one by one under stirring followed by mixing for 30 minutes under ambient temperature to obtain complete homogenize slurry;
(c) adding remaining two active ingredients (Pyroxasulfone and Tembotrione / Mesotrione / Halosulfuron-methyl / Ametryn / Penoxsulam) one by one slowly in step (c) under stirring and mixing for 30 minutes to obtain complete homogeneity;
(d) bead milling the slurry of step (d) to achieve desire particle size to obtain SC form; and
(e) transferring SC form obtain in step (e) into EW form of step (b) followed by homogenizing the mixture of completely to obtain final SE form.

39. A process for preparation of water dispersible granule (WDG/WG) formulation as claimed in claim 33 comprises the steps of;
(a) mixing dispersing agent, wetting agent, buffering agent, binding agent, anti-foaming agent, anti-caking agent, carrier agent, filler and all active ingredients in pre-blender and mixing for 30 min under ambient temperature to complete homogenized;
(b) grinding the pre-blending material of step (a) to achieve desire particle size followed by post blending to obtain homogenize milled premix;
(c) transferring milled premix of step (b) in dough maker to prepare dough followed by spraying DM water under stirring to obtain proper dough; and
(d) transferring dough of step (c) in extruder and collecting granules and charging in dryer at above 50°C temperature to obtain WDG formulation.

40. A process for preparation of Wettable Powder (WP) formulation as claimed in claim 34 comprises the steps of;
(a) Charging dispersing agent, wetting agent, anti-foaming agent, anti-caking agent, carrier agent, filler and active ingredients in pre-blender and mixing form 30 minutes under ambient temperature to complete homogenized; and
(b) grinding the pre-blending material of step (a) to achieve desire particle size followed by post blending the homogenize milled premix to obtain WP formulation.

41. A process for preparation of Emulsion Concentrate (EC) formulation as claimed in claim 35 comprises the steps of;
(a) charging solvent in reactor fitted with stirrer and adding all three active ingredients one by one under stirring and dissolve completely; and
(b) adding stabilizer and emulsifier to step (a) and homogenize the mixture completely to obtain EC formulation.

42. A process for preparation of Oil Dispersion (OD) formulation as claimed in claim 36 comprises the steps of;
(a) Charging carrier agent in reactor fitted with high-speed stirrer and adding wetting agent, dispersing agent, emulsifier and preservative one by one;
(b) adding all three active ingredients one by one slowly in step (a) under stirring and mixing thru high speed stirring for 30 min under ambient temperature to complete homogenized;
(c) adding rheology modifier to step (b) and stirring to obtain homogenize mass as OD formulation.

43. The synergistic herbicidal formulation as claimed in claim 37 to 40; wherein said particle size of active ingredients is maintained between 0.5 to 50 microns.

44. The synergistic herbicidal formulation as claimed in claim 1; wherein said formulation can be applied as pre-emergent and post-emergent treatment.

45. A method of effective removal or control of growth of weeds and undesirable vegetation in broadleaf weeds, narrowleaf weeds, turf weeds, sedges and annual and perennial grasses by applying synergistic herbicidal formulation comprising; (A) Pyroxasulfone in an amount of 2 to 45%; (B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40%; (C) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% along with one or more agrochemically acceptable adjuvants/excipients in an amount of 0.1 to 40% by weight of total formulation.

46. The method of effective removal or control of growth of weeds and undesirable vegetation as claimed in claim 45; wherein said broadleaf weeds include Giant Pigweed/Black Pigweed (Trianthema spp), Prostrate pigweed (Amaranthus spp.), Chickweed (Stellaria media), Dandelion (Taraxacum officinale), Florida betony (Stachys floridana), Japanese clover (Lespedeza striata), broadleaf plantain (Plantago major) and Common vetch (Vicia sativa).

47. The method of effective removal or control of growth of weeds and undesirable vegetation as claimed in claim 45; wherein said grass weeds include Wild rice (Echinochloa colonum), Bermuda grass (Cynodon dactylon), Crabgrass (Digitaria spp), Quackgrass, Doveweed, Dallisgrass, Nutsedge, Bluegrass (Poa annua) and Goosegrass.

48. The method of effective removal or control of growth of weeds and undesirable vegetation as claimed in claim 45; wherein said turf weeds include annual bluegrass, birdsfoot trefoil, black medic, buckhorn plantain, common mallow, common purslane, field paspalum, fountain grass, goose grass, ground ivy, henbit, large crab grass, mouse ear chickweed, nimble will, orchard grass, pineapple weed, prostrate knotweed, prostrate spurge, purple deadnettle, quack grass, roughstalk blue grass, smooth crabgrass, tall fescue, white cover, wild garlic, wild violets and yellow nutsedge.

49. The method of effective removal or control of growth of weeds and undesirable vegetation as claimed in claim 45; wherein said sedges include annual sedge, green kyllinga, purple nutsedge, yellow nutsedge, Cyperus alternifolius (Umbrella Palm), Cyperus compressus (Poor Land Flat Sedge), Cyperus difformis, Cyperus exaltatus, Cyperus haspan, Cyperus iria, Cyperus laevigatus, Cyperus rotundus (Common Nut Sedge, Moth), Cyperus squarrosus, Fimbristylis ovate, Kyllinga nemoralis (White Water Sedge) and Pycreus polystachyos.

50. The method of effective removal or control of growth of weeds and undesirable vegetation as claimed in claim 45; wherein said annual and perennial grasses include annual blue-eyed grass, annual bluegrass, annual ryegrass, bahiagrass, bermuda grass, blue-eyed grass, common dayflower, crowfoot grass, crow-poison, dallis grass, dove weed, goose grass, johnson grass, jungle rice king ranch bluestem, large crabgrass, ohio spiderwort, prairie nymph, prairie spiderwort, red sprangletop, rescuegrass sandbur, smooth crabgrass, smutgrass, spring starflower and wild onion.

51. The method of effective removal or control of growth of weeds and undesirable vegetation as claimed in claim 45; wherein said non-agricultural land include turfgrass, pastures, grasslands, rangelands, fallow land, aquatic settings, wildlife management areas or rangeland.

52. A method of effective removal or control of growth of weeds and undesirable vegetation in crops/fruits/vegetables by applying synergistic herbicidal formulation comprising; (A) Pyroxasulfone in an amount of 2 to 45%; (B) at least one herbicide selected from Topramezone, Tembotrione, Cyhalofop-butyl and Mesotrione in an amount of 0.5 to 40%; (C) at least one herbicide selected from Halosulfuron-methyl, Ametryn, Propaquizafop and Penoxsulam in an amount of 3 to 70% along with one or more agrochemically acceptable adjuvants/excipients in an amount of 0.1 to 40% by weight of total formulation.

53. The method of effective removal or control of growth of weeds and undesirable vegetation as claimed in claim 52; wherein said crops include soyabean (Glycine max), rice/paddy (Oryza sativa), sugarcane (Saccharum officinarum), corn/maize (Zea mays), Sorghum (Sorghum bicolor), Pearl millet (Pennisetum glaucum), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Tea (Camellia sinensis) and Coffea (Coffea Arabica).

54. The method of effective removal or control of growth of weeds and undesirable vegetation as claimed in claim 52; wherein said fruits include Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum), Sapota (Manilkara zapota) and Coconut (Coco nucifera).

55. The method of effective removal or control of growth of weeds and undesirable vegetation as claimed in claim 52; wherein said vegetables include solanaceous vegetables such as eggplant, tomato, pimento, popper, potato, etc., cucurbit vegetables such as cucumber, pumpkin, zucchini, water melon, melon, squash, etc., cruciferous vegetables such as radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower, etc., asteraceous vegetables such as burdock, crown daisy, artichoke, lettuce, etc, liliaceous vegetables such as green onion, onion, garlic, and asparagus, ammiaceous vegetables such as carrot, parsley, celery, parsnip, etc., chenopodiaceous vegetables such as spinach, swiss chard, etc., lamiaceous vegetables such as Perilla frutescens, mint, basil, etc. strawberry, sweet potato, Dioscorea japonica and colocasia.