DESC:FIELD OF THE INVENTION:
The present subject matter relates to herbicidal compositions for controlling undesired vegetation. Specifically, the present subject matter relates to herbicidal compositions comprising a synergistic combination of Propaquizafop and co-herbicides, wherein co-herbicide may be selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, and Chloransulam methyl. The present invention also relates to process for preparing the said herbicidal compositions comprising Propaquizafop and a coherbicide wherein the said herbicides may be selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, Chloransulam methyl and at least one agrochemically acceptable excipient.
BACKGROUND OF THE INVENTION

The control of undesired vegetation is extremely important in order to achieve high crop efficiency. In many cases, herbicides have an effect against a spectrum of weeds; however, these herbicides may not be effective certain type of other weeds, which may also be present in the crop to be protected. Therefore, there is a strong need for composition of two or more herbicides.

Herbicidal compositions of the present invention have several advantages over the use of a single herbicide including (a) an increase in the spectrum of weeds controlled or an extension of weed control over a longer period of time, (b) an improvement in crop safety by using minimum doses of selected herbicides applied in combination rather than a single high dose of one herbicide and (c) a delay in the appearance of resistant weed species to selected herbicides {Int. J. Agri. Biol., Vol. 6, No. 1, 2004, pages 209-212).

Herbicide(s), also commonly known as weed killers, used to kill unwanted plants. Selective herbicides kill specific targets, while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of the weed and are often synthetic mimics of natural plant hormones. Herbicides can be non-selective and kill all plant material with which they come into contact. Smaller quantities are used in forestry, pasture systems, and management of areas set aside as wildlife habitat.

Some plants produce natural herbicides, such as the genus Juglans (walnuts), or the tree of heaven; such action of natural herbicides, and other related chemical interactions, is called allelopathy.

Prior to the widespread use of chemical herbicides, cultural controls, such as altering soil pH, salinity, or fertility levels were used to control weeds. Mechanical control (including tillage) was also (and still is) used to control weeds.

Herbicides are classified by their mode of action, they are listed below:
ACCase Inhibitors: They belong to Arloxyphenoxy propionate (FOPS) chemical family which blocks the first step in fatty acid synthesis in grasses; broadleaves are naturally resistant to the fops and dims due to an insensitive ACCase enzyme.
ALS Inhibitors: They belong to Sulfonylurea, Imidazonlinone and Pyrimidineschemical family which blocks the production of branched chain amino acids (isoleucine, leucine, and valine) in the plant. Plant dies from insufficient branched chain amino acid levels.
Microtubule Protein Inhibitor: They belong to Dinitroaniline chemical family which interferes with the alignment of the spindle apparatus during mitosis and prevents normal cell division in root tissue.
Synthetic Auxins: They belong to Phenoxy, Benzoic Acid and Carboxylic Acid chemical group which synthetic auxinsmimic the natural plant hormone IAA. These herbicides affect cell wall plasticity and nucleic acid metabolism which leads to inhibited cell division and growth in the meristem regions (growing points).
Photosystem II Inhibitor : They belong to Triazine, Triazinone, Nitriles, Benzothiadiazinones and Ureas chemical families wherein PS II herbicides inhibit photosynthesis by binding to the QB-binding niche on the D1 protein of the photosystem II complex in the chloroplast. It blocks electron flow from QA to QB and stops CO2 fixation and production of ATP and NADPH2 which are needed for plant growth and development. Death occurs from free radicals destroying cell membranes.
EPSP Synthase Inhibitor: They belong to Glycines chemical family which inhibit EPSP synthase enzyme which leads to the depletion of the aromatic amino acids tryptophan, tyrosine, and phenylalanine.
Glutamine Synthesis Inhibitor: They belong to Phosphinic Acids chemical family which inhibits the activity of glutamine synthetase which converts glutamate and ammonia to glutamine. Accumulation of ammonia to lethal levels destroys plant cells and tissue.
DOXP synthase Inhibitor: They belong to Isoxazolidinone chemical family which inhibits the 1-deoxy-D-xyulose 5-phosphate synthase (DOXP), a key component to the plastid isoprenoid synthesis.
HPPD inhibitor : They belong to Pyrazole and Triketone chemical families which inhibit the 4-hydroxyphenyl-pyruvate dioxygenase (4-HPPD) which affects carotenoid biosynthesis. Both herbicide families deplete the carotenoid (accessory pigments) pool that protects chlorophyll in the plant which results in a characteristic bleaching of the plant tissue
PPO inhibitors: They belong to Diphenylether, N-phenylphthalimide and Arytriazinone chemical family which inhibit the photoporphyrinogen oxidase (PPO), an enzyme that is responsible for chlorophyll and heme biosynthesis. PPO inhibition leads to accumulation of PPIX (protoporphyrin IX) which creates free radical oxygen in the cell and destroys cell membranes.
VLFA inhibitors: They belong to Chloroacetamide chemical family which inhibits very longchain fatty acid synthesis (VLFA) in shoot tissue during germination of sensitive plants.
Photosystem I Inhibitor: They belong to Bipyridyliums chemical family which capture electrons from photosystem I and are reduced to form herbicide free radicals. These free radicals destroy cell membranes.

Propaquizafop was first disclosed in US 4687849 A. IUPAC name of propaquinazop is (R)-2-[4-[(6-Chloro-2-quinoxalinyl)oxy]phenoxy] propanoicacid 2-[[(1-methylethylidene) amino] oxy]ethyl ester and chemical structure is as below.

Propaquizafop is a chemical compound from the group of quinoxalines. Propaquizafop is used as an herbicide for selective weed control in the post-emergence against a wide range of annual and perennial grasses in sugar beets, canola, soybean, sunflower, other crops, vegetables, fruit trees, wine and forestry. [6] The effect is due to inhibition of the acetyl-CoA carboxylase (ACCase).

Propaquizafop is a systemic herbicide, which is quickly absorbed by the leaves and translocated from the foliage to the growing points of the leaves and roots of the sprayed weeds.

One of the main concerns of herbicide is weed resistance and has become a major concern in crop production worldwide. Resistance to herbicides is often attributed to lack of rotational programmes of herbicides and to continuous applications of herbicides with the same sites of action. Thus, a true understanding of the sites of action of herbicides is essential for strategic planning of herbicide-based weed control. Further Propaquizafop is effective only on monocot weeds where as in field, growers’ needs to do tank mix with broad leaf weed killer herbicide for control of dicot weeds. This tank mixing method is not suitable and also causes many problems like safety concern, resistance issue etc.

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

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

WO 2000027203 A1 patent discloses herbicidal synergistic composition for controlling broad-leaved weeds and grasses in crops of useful plants resistant to protoporphyrinogen oxidase inhibitors, comprising, in addition to customary inert formulation auxiliaries, as active compounds a) a herbicide which inhibits the action of protoporphyrinogen oxidases and b) at least one further pesticide selected from the group consisting of co-herbicides, fungicides and insecticides/acaricides.

EP 1605760 A2 patent discloses synergistic herbicidal mixture comprising: A) [N-(5,7-Dimethoxy[1,2,4]triazolo[1,5-a]pyrimidin-2-yl)-2-methoxy-4-(trifluoromethyl)]-3-pyridinesulfonamid (I) or one of its environmentally compatible salts; B) and at least one herbicidal compound from the group and at least one compound from the group of the safeners.

DE 19834629 A1 patent discloses A herbicidal composition contains, apart from conventional inert formulation auxiliaries, an active agent combination of: (A) pretilachlor, cinosulfuron, triasulfuron, fenclorim, clodinafop-propargyl, metolachlor, S-metolachlor, fluometuron, prometryn, norfluorazon, propaquizafop, trinexapac, atrazine, ametryn, dicamba, terbutryn, prosulfuron, norflurazon, terbuthylazine, simazine, prosulfuron, primisulfuron, oxasulfuron, fluthiacet-methyl, clodinafop, cloquintocet-mexyl, prometryn or dimethachlor; and (B) one or more selected from bensulfuron, imazosulfuron, pyrazosulfuron, metsulfuron, azimsulfuron, cyclosulfamuron, esprocarb, mefenacet, molinate, propanil, pyrazolate, cyhalofop-butyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, bispyribac, bispyribac-sodium, pyriminobac-methyl, cafenstrole, dymron, NB061, indanofan, HW-52, oxadiargyl, glyphosate, S-glufosinate, glufosinate, sulfosate, halosulfuron-methyl, clomazon, oxadiazon, mefenpyr, cyhalofop-butyl, pyrithiobac, pyrithiobac-sodium, triflur alin, pendimethalin, bromoxynil, clomazone, MSMA, DMSA, fluazifop-butyl, fluazifop-P-methyl, quizalofop-ethyl, quizalofop-P-ethyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, sethoxydim, clethodim, diuron, cyanazine, alachlor, acetochlor, flurochloridone, ipconazole, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl, spiroxamine, mepronil, myclobutanil, nuarimol, pefurazoate, pencycuron, phthalide, probenazole, prochloraz, prozymidone, propiconazole, pyrazophos, pyroquilon, quinoxyfen, quintozene, minostrobin, meto, tebuconzole, tetraconazole, thiabendazole, thifluzamide, triadimefon, triadimenol, tricyclazole, tridemorph, triflumixole, triforine, triticonazol, vinclozolin, chlormequat chloride, clofencet, cyclanilide, ethephon, flurprimidol, gibberellic acid, inabenfide, maleic hydrazide, mefluidide, mepiquat chloride, paclobutrazol, prohexadion-calcium, uniconazole, thidiazuron, amidosulfuron, azimsulfuron, bbensulfuron, bromoxynil, carfentrazone-ethyl, chlorsulfuron, cinosulfuron, clodinafop-propargyl, cyclosulfamuron, cyhalofop-butyl, dicamba, diclofop-methyl, diflufenican, fluazolate, flucarbazone, flufenacet, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluroxypyr, flurtamone, imazosulfuron, indanofan, iodosulfuron, isoproturon, MCPA, MCPB, mecoprop-P, metsulfuron, pyrazosulfuron, sulfasulfuron, thifensulfuron, tribenuron, 2,4-D, benfuresate, bentazone, bifenox, bromobutide, dichlorprop-P, dithiopyr, ethametsulfuron, flamprop-M, fluoroglycofen, halosulfuron, imazamethabenz, ioxynil, mefenacet, methyldymron, metosulam, pyridate, quinoclorac, quinmerac, thiazopyr, traloxydim, paraquat, hexazinone, asulam, diuron, MCPA, halosulfuron, flazasulfuron, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, aciflurofen, aminotriazole, azafenidin, carfentrazone-ethyl, diquat, diuron, flazasulfuron, flumioxazin, fluroxypyr, alloxydim, butroxydim, clethodim, cloproxydim, cycloxydim, cyhalofop-butyl, diclofop-methyl, fluazifop-P-butyl, fenoxaprop-P-ethyl, fenthiaprop-P-ethyl, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P-methyl, quizalofop, quizalofop-P-ethyl, sethoxydim, fenoxaprop-P-ethyl, fenthiaprop-p-ethyl, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P-methyl, quizalofop-P-ethyl, sethoxydim, tepraloxydim (BAS 20H; originally caloxydim), tralkoxydim, sunflower, pendimethalin, aclonifen, flurochloridon, alloxydim, butroxydim, clethodim, cloproxydim, cyloxydim, diclofop-methyl, fluazifop-butyl, fenoxaprop-P-ethyl and the compounds of formulae (I)-(IV).

WO 2013106543 A3 patent discloses Herbicidal compositions comprising (a) bentazon-sodium and (b) an ALS inhibitor and (c) an ACCase inhibitor that controls susceptible and resistant weeds in crops.

US 8921268 B2 patent discloses a herbicidal composition including as active ingredients isoxaflutole, cyprosulfamide, and one or more compounds selected from Group A has weed control effects.

Inventors of the present invention have surprisingly found that the synergistic compositions of Propaquizafop with a co-herbicide as described herein in can provide solution to the above problems.

SUMMARY OF THE INVENTION

The present invention is all about synergistic herbicidal compositions of Propaquizafop from and co- herbicides, wherein co- herbicide may at least be selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, and Chloransulam methyl.

The present invention also relates to process for preparing the said herbicidal compositions comprising Propaquizafopand a co- herbicide wherein the said herbicides may at least be selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, and Chloransulam methyl.

According to the present invention, the ratio of Propaquizafop to Fomesafen is 1:25 to 5:1, Propaquizafop to lactofen is 1:25 to 5:1, Propaquizafop to Aciflurofen is 1:25 to 5:1, Propaquizafop to Bentazon is 1:25 to 5:1, and Propaquizafop to Chloransulam methyl is 1:25 to 5:1.

Further the present invention also relates to the process for preparing the said synergistic compositions of Propaquizafop with a co- herbicide and at least one agrochemically acceptable excipient.

According to yet another aspect there is provided a method of controlling undesired vegetation comprising applying to the locus of the undesired vegetation a herbicidally effective amount of the composition comprising Propaquizafop esters, salts and/or combination thereof and a co- herbicide.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides synergistic herbicidal compositions of Propaquizafop and co-herbicides, wherein co- herbicide may be selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, Chloransulam methyl and at least one agrochemically acceptable excipient.

Synergism is the cooperative action encountered in combinations of two or more herbicide compounds in which the combined activity of the two compounds exceed the sum of the activities of the compounds when used alone.

The present subject matter relates to herbicidal compositions comprising Propaquizafop and a co- herbicide combination thereof.

An embodiment relates to synergistic herbicidal compositions comprising Propaquizafop, esters, salts and co- herbicide and/or combination thereof. In an embodiment, the ratio of Propaquizafop to Fomesafen is 1:25 to 5:1, Propaquizafop, Propaquizafop to Lactofen is 1:25 to 5:1, and of Propaquizafop to Aciflurofen is 1:25 to 5:1, Propaquizafop to Bentazon is 1:25 to 5:1, and Propaquizafop to Chloransulam methyl is 1:25 to 5:1.

In another embodiment, a composition comprising Propaquizafop and a co- herbicide including esters and salts thereof and an agriculturally acceptable carrier, is provided.

The compositions may include additional other crop protection agents, for example pesticides, safeners or agents for controlling phytopathogenic fungi or bacteria.

All technical and scientific terms used herein have the same meanings as commonly understood by someone ordinarily skilled in the art to which the present subject matter belongs. The following definitions are provided for clarity. As used herein the term "crop" includes reference to whole plant, plant organ (e.g., leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), or plant cells.

As used herein the term "locus" includes not only areas where weeds may already be growing, but also areas where weeds have yet to emerge, and also to areas under cultivation.

As used herein the term "agriculturally acceptable carrier" means carriers of which are known and accepted in the art for the formation of formulations for agricultural or horticultural use.

The term "surfactant," as used herein, refers to an agriculturally acceptable material which imparts emulsifiability, stability, spreading, wetting, dispersibility or other surface-modifying properties.

The term "a" or "an" as used herein includes the singular and the plural, unless specifically stated otherwise. Therefore, the term "a," "an," or "at least one" can be used interchangeably in this application.

Throughout the application, descriptions of various embodiments use the term "comprising;" however, it will be understood by one of skill in the art, that in some specific instances, an embodiment can alternatively be described using the language "consisting essentially of or "consisting of."

For the purposes of better understanding the present teachings and in no way limiting the scope of the teachings, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

The preferred co-herbicides as used herein, are selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, Chloransulam methyl and salts thereof, wherein the salts of co-herbicide include, but are not limited to: potassium, sodium or like alkali metals, and salts of calcium, magnesium, barium or like alkaline earth metals, or pyridinium salt.

In an embodiment, the present synergistic compositions of Propaquizafop and one more co-herbicide selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, and Chloransulam methyl may be applied pre-plant incorporated, pre- or post-emergence. In an embodiment, the herbicidal compositions may be applied on crops which include and plants like Soybean (Glycine max), Peanut or Groundnut (Arachishypogaea), Mung bean or Green gram (Vignaradiata), Urad or Black gram (Vignamungo), Pegion pea or Red gram (Cajanuscajan), Bengal gram or Chickpea (Cicerarietinum), Rajma or French bean (Phaseolus vulgaris), Clusterbean (Cyamopsistetragonaloba), Cowpea (Vignaunguiculata), field peas, snap bean, alfalfa, lettuce, beans.

In an embodiment, the present synergistic compositions of Propaquizafop and one more co-herbicide selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, and Chloransulam methyl will be effective in controlling weeds like Monocotyledon weeds or grassy weeds of the genera such as Barnyard grass (Echinochloa spp.), Crabgrass (Digitaria spp.), Goosegrass (Eluesineindica), Millet grass (Panicumjavanicum), Foxtail (Setariaverticiliata), Bermuda grass (Cynodondactylon), Sorghum (Sorghum halepenses), Crow footgrass (Dactylocteniumaegyptium), Rottboelliacochinchinesis, Saccharumspontaneum, , Brachiariaarvensis. Dicotyledon weeds or broad leaved weeds of the genera such as Day flower (Commelinabenghalensis and Commelinasinensis), Pigweeds (Amaranthusviridis and Amaranthuslividis), Purslane (Portulacaoleracea), Morning glory (Ipomoea spp.), Nightshade (Solanum spp.), Spurge (Euphorbia geniculata and Euphorbia hirta), Ragweed (Ambroasia spp.), Small melon (Cucumis spp.), Starbur (Acanthospermum spp.), Cocklebur (Xanthium strumarium), Ground cherry (Physalis minima), Kotweed (Polygonum spp.), Thomapple (Datura spp.), Acalyphaindica, Wild jute (Corchorus), Digeraarvensis, Partheniumhysterophorus, Phyllanthusniruri, Alternantheraphiloxeroides, Trainthemaportulacastrum, Cyanotiscuculata, Cyanotisaxillaris, Lactucaruncinata, Boerhaviadiffusa, Hibiscus trionum, Loliumperenne L. ssp. multiflorum (Lam.) Husnot, Sidarhombifolia L., Anodacristata (L.) Schlecht.,Lamium spp. L, Cyperus di formis L., Croton sperrsifeorus, Nicandraphysalodes, Chenopodium album L.,

The described compositions may be made at the time of use, or diluted, or else they can be concentrated compositions, or so-called "ready-to-use" compositions, that is to say, ready for marketing. In an embodiment, the formulation may be obtained by combining a synergistic amount of the active ingredients with an agriculturally acceptable carrier, a surfactant or other application-promoting adjuvant customarily employed in formulation technology.

In yet another embodiment, the compositions may be employed in any conventional form, for example, in the form of a twin pack, or as emulsion concentrates (EC), microemulsion concentrates (MEC), suspension concentrates (SC), soluble concentrates (SL), suspoemulsion (SE), oil dispersions (OD), water dispersible granules (WDG), water soluble granules (SG) and wettable powders (WP). Such compositions can be formulated using with agriculturally acceptable carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology and formulation techniques that are known in the art. Preferably the herbicidal composition of the present invention is in the form of Oil Dispersion (OD).

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

The main active ingredient is Propaquizafop which can be further combined with a co-herbicide selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, Chloransulam methyl and its salts thereof. Wherein the salts of co-herbicide include, but are not limited to: potassium, sodium or like alkali metals, and salts of calcium, magnesium, barium or like alkaline earth metals, or pyridinium salt.

The present invention also relates to preparing the said herbicidal compositions comprising Propaquizafop and a co- herbicide wherein the said herbicides may be selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, and Chloransulam methyl. According to the present invention, the ratio of Propaquizafop to Fomesafen is 1:25 to 5:1, Propaquizafop to Lactofen is 1:25 to 5:1 and of Propaquizafop to Aciflurofen is 1:25 to 5:1, Propaquizafop to Bentazon is 1:25 to 5:1, Propaquizafop to Chloransulam methyl is 1:25 to 5:1.

The synergistic herbicidal composition of the present invention in addition to Propaquizafop and a coherbicide selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, and Chloransulam methyl further comprises one or more inactive excipients including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.

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

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

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

Adjuvants are added to enhance field activity of OD formulation upon dilution with water; it will enhance the uniform spreading of spray solution over foliage which lead to high absorption through leaf cuticle. The example of this adjuvant is Polyalkyleneoxide modified heptamethyl trisiloxane.

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

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

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

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

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

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

Oil dispersion (OD) formulation may be prepared by below mentioned general process;
The organic solvent is charged into a vessel and the clay or silica type rheology modifier is added into the vessel with high shear mixing to allow complete wetting of the rheology modifier. The insecticide, safener, dispersants, and emulsifier may then be added to the vessel under shearing conditions until the formation of uniform oil dispersion is achieved. The polymer or oligomer capable of hydrogen bonding may be introduced into the oil dispersion at a point where the desired thickening effect is achieved.

We have developed novel formulation of Oil Dispersion by adding adjuvant that enhances the field activity of OD formulation upon dilution with water; this will enhance the uniform spreading of spray solution over foliage which leads to high absorption through leaf cuticle.
Examples of suitable liquid carriers to be used in the composition may include water, aromatic hydrocarbons such as alkylbenzenes and alkylnaphthalenes, alcohols such as methanol, cyclohexanol and decanol, ethylene glycol, polypropylene glycol and dipropropylene glycol, N,N-dimethylformamide, dimethylsulfoxide, N- alkylpyrrolidone, paraffins, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone and the like.

Examples of suitable solid carriers to be used in the composition may include mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, sodium carbonate and bicarbonate, and sodium sulfate, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

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

EXAMPLES
Example 1: Propaquizafop 6.25% + Sodium salt of Fomesafen 18% OD (Oil Dispersion)
Composition % w/w
Propaquizafop (95%) 6.84
Sodium Salt of Fomesafen (47%) 39.36
Ethoxylated Oleyl-Cetyl Alcohol 5.00
Tris(2-ethylhexyl)phosphate 10.00
Polyvinylpyrrolidone 3.50
Calcium alkyl benzene sulfonate 2.50
Castor oil ethoxylates 3.50
Silicon based antifoam 0.50
Polyester block co-polymer 3.00
Polyalkyleneoxide modified heptamethyltrisiloxane 2.00
Methylated Soyabean oil 23.80
TOTAL 100.00

Procedure:
Step 1 Charge required quantity of vegetable oil in vessel and add polyvinyl pyrrollidone, mix well for 30 minutes using high shear homogenizer and pass through horizontal bead mill.
Step 2 Add required quantity of Wetting agent, dispersing agent & suspending agents and homogenize the contents for 45 – 60 minutes using high shear homogenizer.
Step 3 Then add technical materials and homogenize for further 30 minutes.
Step 4 Now pass this homogenized material through horizontal bead mill to get required particle size.
Step 5 Now add the Polyester block co-polymer into this milled mixture and homogenized for 30 minutes.
Step 6 After completion of grinding cycles sample is sent to QC for A.I. & particle size analysis
Step 7 After approval from QC, Polyalkyleneoxide modified heptamethyltrisiloxane is added to material.
Step 8 After final addition if sample is sent to QC for final approval and on approval material is transferred to holding vessel for packing

Example 2: Propaquizafop 6.25% + Sodium salt of Fomesafen 18% OD (Oil Dispersion)
Composition % w/w
Propaquizafop (95%) 6.84
Sodium Salt of Fomesafen (47%) 39.36
Ethoxylated Oleyl-Cetyl Alcohol 5.00
Tris(2-ethylhexyl)phosphate 10.00
Polyvinylpyrrolidone 3.50
Calcium alkyl benzene sulfonate 2.50
Castor oil ethoxylates 3.50
Silicon based antifoam 0.50
Polyester block co-polymer 3.00
Polyalkyleneoxide modified heptamethyltrisiloxane 2.00
Methylated Soyabean oil 23.80
TOTAL 100.00
Procedure: As per Example 1

Example 3: Propaquizafop 5% + Lactofen 15% OD (Oil Dispersion)
Composition Normal %
Propaquizafop (95%) 5.80
Lactofen (85%) 18.50
Ethoxylated Oleyl-Cetyl Alcohol 5.00
Tris(2-ethylhexyl)phosphate 10.00
Polyvinylpyrrolidone 3.50
Calcium alkyl benzene sulfonate 2.50
Castor oil ethoxylates 3.50
Silicon based antifoam 0.50
Polyester block co-polymer 3.00
Polyalkyleneoxide modified heptamethyltrisiloxane 2.00
Methylated Soyabean oil 45.70
TOTAL 100.00

Procedure: As per Example 1

Example 4: Propaquizafop 5% + Acifluorfen 13% OD (Oil Dispersion)
Composition w/w %
Propaquizafop (95%) 5.80
Sodium salt of Acifluorfen (44%) 30.70
Ethoxylated Oleyl-Cetyl Alcohol 5.00
Tris(2-ethylhexyl)phosphate 10.00
Polyvinylpyrrolidone 3.50
Calcium alkyl benzene sulfonate 2.50
Castor oil ethoxylates 3.50
Silicon based antifoam 0.50
Polyester block co-polymer 3.00
Polyalkyleneoxide modified heptamethyltrisiloxane 2.00
Methylated Soyabean oil 33.50
TOTAL 100.00
Procedure: As per Example 1

Example 5: Propaquizafop 1.3% + Bentazon 19% OD (Oil Dispersion)
Composition Normal %
Propaquizafop (95%) 1.90
Bentazone Sodium Salt (60%) 32.50
EthoxylatedOleyl-Cetyl Alcohol 5.00
Tris(2-ethylhexyl)phosphate 10.00
Polyvinylpyrrolidone 3.50
Calcium alkyl benzene sulfonate 2.50
Castor oil ethoxylates 3.50
Silicon based antifoam 0.50
Polyester block co-polymer 3.00
Polyalkyleneoxide modified heptamethyltrisiloxane 2.00
Methylated Soyabean oil 35.60
TOTAL 100.00

Procedure: As per Example 1

Example 6: Storage stability data
6.1: Storage stability Study Data of Propaquizafop 6.25% + Sodium salt of Fomesafen 18% OD (Oil Dispersion) of Example 2
Specification Initial Heat stability study at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description Off-white to Yellowish to flowable liquid Complies Complies Complies
Propaquizafop Content 5.937 - 6.875 6.29 6.05 6.28
Propaquizafop Suspensibility Mini 80% 95 95 95
Fomesafen Content 17.100 - 18.900 18.19 18.03 18.15
Fomesafen Suspensibility Mini 80% 96 94 96
pH 4.5-7.0 6 6 5.8
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1
Viscosity 300-900 500 550 600

Room temperature storage data
Specification Study Duration
Parameters In house 3 month 6 month 9 month 12 month
Description Off-white to Yellowish to flowable liquid Complies Complies Complies Complies
Propaquizafop Content 5.937 - 6.875 6.29 6.29 6.29 6.19
PropaquizafopSuspensibility Mini 80% 95 95 95 95
Fomesafen Content 17.100 - 18.900 18.19 18.19 18.17 18.15
FomesafenSuspensibility Mini 80% 96 96 96 96
pH 4.5-7.0 6 6 6 6
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1 1.1
Viscosity 300-900 500 500 500 500

6.2: Storage stability Study Data of Propaquizafop 5% + Lactofen 15% OD (Oil Dispersion)
Specification Initial Heat stability study at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description Off-white to Yellowish to flowable liquid Complies Complies Complies
Propaquizafop Content 4.75-5.5 5.5 5.4 5.5
Propaquizafop Suspensibility Mini 80% 95 95 95
Lactofen Content 14.25 - 15.75 15.5 15.3 15.5
Lactofen Suspensibility Mini 80% 96 94 96
pH 4.5-7.0 6 6 5.8
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1
Viscosity 300-900 500 550 600

Room Temperature Storage data
Specification Study Duration
Parameters In house 3 month 6 month 9 months 12 months
Description Off-white to Yellowish to flowable liquid Complies Complies Complies Complies
Propaquizafop Content 4.75-5.5 5.5 5.5 5.5 5.5
PropaquizafopSuspensibility Mini 80% 95 95 95 95
Lactofen Content 14.25 - 15.75 15.5 15.5 15.5 15.5
LactofenSuspensibility Mini 80% 96 96 96 96
pH 4.5-7.0 6 6 6 6
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1 1.1
Viscosity 300-900 500 500 500 500

6.3: Storage stability Study Data of Propaquizafop 5% + Acifluorfen 13% OD (Oil Dispersion)
Specification Initial Heat stability study at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description Off-white to Yellowish to flowable liquid Complies Complies Complies
Propaquizafop Content 4.75-5.5 5.5 5.3 5.5
Propaquizafop Suspensibility Mini 80% 95 95 95
Acifluorfen Content 12.35-13.65 13.5 13.2 13.45
Acifluorfen Suspensibility Mini 80% 96 94 96
pH 4.5-7.0 6 6 5.8
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1
Viscosity 300-900 500 550 600

Room Temperature Storage Data
Specification Study Duration
Parameters In house 1 month 3 month 6 month 9 month 12 month
Description Off-white to Yellowish to flowable liquid Complies Complies Complies Complies Complies
Propaquizafop Content 4.75-5.5 5.5 5.5 5.5 5.5 5.5
Propaquizafop Suspensibility Mini 80% 95 95 95 95 95
Acifluorfen Content 12.35-13.65 13.5 13.5 13.5 13.5 13.5
AcifluorfenSuspensibility Mini 80% 96 96 96 96 96
pH 4.5-7.0 6 6 6 6 6
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1 1.1 1.1
Viscosity 300-900 500 500 500 500 500

6.4: Storage stability Study Data of Propaquizafop 1.3% + Bentazon 19% OD (Oil Dispersion)

Specification Initial Heat stability study at 54+2 0C for 14 days Cold storage stability at 0+2 0C for 14 days
Parameters In House
Description Off-white to Yellowish to flowable liquid Complies Complies Complies
Propaquizafop Content 1.235-1.43 1.4 1.3 1.4
PropaquizafopSuspensibility Mini 80% 95 95 95
Bentazon Content 18.05-19.95 19.5 19.3 19.44
BentazonSuspensibility Mini 80% 96 94 96
pH 4.5-8.0 6.5 6.5 6.5
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1
Viscosity 300-900 500 550 600

Room Temperature Storage Data
Specification Study Duration
Parameters In house 3 month 6 month 9 months 12 months
Description Off-white to Yellowish to flowable liquid Complies Complies Complies Complies
Propaquizafop Content 1.235-1.43 1.4 1.4 1.4 1.4
PropaquizafopSuspensibility Mini 80% 95 95 95 95
Bentazon Content 18.05-19.95 19.5 19.5 19.5 19.5
BentazonSuspensibility Mini 80% 96 96 96 96
pH 4.5-8.0 6.5 6.5 6.5 6.5
Particle size D50 <3, D90 <10 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8 D50 <2.1, D90 <8
Pourability Mini 95% 97 97 97 97
Specific gravity 1.02 – 1.15 1.1 1.1 1.1 1.1
Viscosity 300-900 500 500 500 500

Example 7: Bio efficacy trials

Field Experiments:
Various field experiments of novel formulations of Propaquizafop+Fomesafen, Propaquizafop+Acifluorfen, Propaquizafop+Lactofen were conducted on various crops like soybean, peanut and black gram.
Trial 1:Phytotoxicity and Bioefficacy evaluation on soybean crop
The field experiment was conducted on soybean and experimental details as below:
Crop &Variety: Soybean, JS 335
Experimental design: Randomized block design
Replications: Four
No. of Treatments: Five
Plot size: 40 sq. mt.
Application Time: 22 DAS (Days after sowing)
Observations: For phytotoxicity – 3, 7, 15 and 20 DAA (Days after Application)
For Bioefficacy- 15 and 30 DAA (Days after Application)
Water Volume: 375 liter per hectare
Application Equipment: Manually operated knap sack sprayer fitted with flat fat nozzle
Experimental Methodology:
Soybean crop was raised as per the standard agronomic practices in the field. The herbicidal application of novel formulation of Propaquizafop 6.25%+Fomesafen 18% OD, Propaquizafop 10% EC, Sodium salt of Fomesafen 22.1% SL and tank mix of Propaquizafop 10% EC + Sodium salt of Fomesafen 22.1% SL were done at 22 DAS (vegetative growth stage) with the help of manual operated knap sack sprayer. The untreated plot was also sprayed with water only. The phytotoxicity observations i.e. leaf scorching were recorded by adopting 0-10 rating scale as below:
0= No phytotoxicity, 1 =1-10% leaf scorching, 2=11-20% leaf scorching, 3=21-30% leaf scorching, 4=31-40% leaf scorching, 5=41-50% leaf scorching, 6=51-60% leaf scorching, 7=61-70% leaf scorching, 8=71-80% leaf scorching, 9=81-90% leaf scorching, 10=91-100% leaf scorching.
Percent phytotoxicity was calculated by following formula:
Sum of all scores
% Phytotoxicity = -------------------------------------------------------- x 100
Number of samples x Highest rating scale

Bioefficacy observations: Species wise weed count recorded at 15 and 30 DAA (Days after Application) by using 50cm x 50 cm quadrant treatment wise in 4 places randomly selected in plot per replication. The average of each observation was used together with the sum of all the observations per plot to calculate the percentage of control.
The % weed control calculated as follows:

% Weed Control =
Mean weed count in untreated plot – Mean weed control in treated plot
------------------------------------------------------------------------------------------- x 100
Mean weed count in untreated plot

Table 1 Phytotoxicity of novel formulations of Propaquizafop+Fomesafen on Soybean
Sr. No. Treatment Details Formulation (ml/ha) Active Ingredient (g/ha) Leaf Scorching (%)
3 DAA 7 DAA 15 DAA 20 DAA
1 Untreated Check - - 0 0 0 0
2 Propaquizafop 10% EC 625 ml 62.5 0.00 0.00 0.00 0.00
3 Sodium salt of Fomesafen 22.1% SL 815 ml 180 26.62 18.80 14.26 10.42
4 Propaquizafop 10% EC + Sodium salt of Fomesafen 22.1% SL (tank-mix) 625 ml+ 815 ml 62.5+180 28.34 21.72 17.34 12.64
5 Propaquizafop 6.25% + Sodium salt of Fomesafen 18% OD 1000 ml 62.5+180 8.27 5.16 0.00 0.00

The field trial results shows that the novel formulation of Propaquizafop 6.25% + sodium salt of Fomesafen 18% OD found less toxic to the soybean crop compared to their tank mixes.
Table 2 Weed control in Soybean-Tank mix v/s Novel formulations of Propaquizafop+Fomesafen
Sr.No. Treatment Details Formulation (ml/ha) Active Ingredient (g/ha) % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
1 Untreated Check 0 0
2 Propaquizafop 10% EC 625 ml 62.5 60.94 63.72
3 Sodium salt of Fomesafen 22.1% SL 815 ml 180 53.50 55.90
4 Propaquizafop 10% EC + Sodium salt of Fomesafen 22.1% SL (tank-mix) 625 ml + 815 ml 62.5+180 80.24 81.66 81.84 84.00 0.98 0.97
5 Propaquizafop 6.25% + Sodium salt of Fomesafen 18% OD 1000 ml 62.5+180 96.82 98.16 81.84 84.00 1.18 1.17
Weed flora (Grasses – Echinochloacolonum, Digitariasanguinalis, Eleusineindica, Broad leaf weeds – Commelinabenghalensis, Digeraarvensis, Euphorbia geniculata, Phyllanthusniruri)
The efficacy trial results shows that OD formulation of Proapquizafop 6.25%+Sodium salt of Fomesafen 18% shows synergistic activity on weed compared to their tank mixes and also provides more than 98% control of mixed weed flora in soybean crop

Trial 2:Phytotoxicity and Bioefficacy evaluation on Peanut / Groundnut crop
The field experiment was conducted on Peanut and experimental details as below:
Crop & Variety: Peanut, GG-2
Experimental design: Randomized block design
Replications: Four
No. of Treatments: Five
Plot size: 50 sq. mt.
Application Time: 30 DAS (Days after sowing)
Observations: For phytotoxicity – 3, 7, 15 and 20 DAA (Days after Application)
For Bioefficacy- 15 and 30 DAA (Days after Application)
Water Volume: 375 liter per hectare
Application Equipment: Manually operated knap sack sprayer fitted with flat fat nozzle
Experiment Method: As per Example 1
Table 3 Phytotoxicity of novel formulations of Propaquizafop+Acifluorfen on Peanut
Sr. No. Treatment Details Formulation (ml/ha) Active Ingredient (g/ha) Leaf Scorching (%)
3 DAA 7 DAA 15 DAA 20 DAA
1 Untreated Check - - 0 0 0 0
2 Propaquizafop 10% EC 625 ml 62.5 0.00 0.00 0.00 0.00
3 Sodium salt of Acifluorfen20.1% SL 809 ml 162.5 30.62 24.12 16.20 10.52
4 Propaquizafop 10% EC + Sodium salt of Acifluorfen 20.1 % SL (tank-mix) 625 ml+ 809 ml 62.5 + 162.5 34.64 26.60 19.72 13.50
5 Propaquizafop 5% + Sodium salt of Acifluorfen 13% OD (Oil Dispersion) 1250 ml 62.5 + 162.5 10.26 4.24 0.00 0.00
Observation on phytotoxocity study shows that novel formulation Propaquizafop 5%+sodium salt of Acifluorfen 13% OD shows little scorching on Peanut leaf which recovers within 15 days after application.
Table 4 Weed control in Peanut-Tank mix v/s Novel formulations of Propaquizafop+Acifluorfen
Sr.No. Treatment Details Formulation (ml/ha) Active Ingredient (g/ha) % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
1 Untreated Check - - 0 0
2 Propaquizafop 10% EC 625 ml 62.5 56.82 60.26
3 Sodium salt of Acifluorfen20.1% SL 809 ml 162.5 45.82 46.22
4 Propaquizafop 10% EC + Sodium salt of Acifluorfen 20.1 % SL (tank-mix) 625 ml+ 809 ml 62.5 + 162.5 75.42 77.12 76.61 78.63 0.98 0.98
5 Propaquizafop 5% + Acifluorfen 13% OD (Oil Dispersion) 1250 ml 62.5 + 162.5 97.26 98.87 76.61 78.63 1.27 1.26
Weed flora (Grasses – Eragrostis major, Dactylocteniumaegyptium, Dinebraretroflexa, Broad leaf weeds –Amaranthusviridis, Trianthemamonogyna, Physalis minima, Portulacaoleracea)
The synergistic activity of Propaquizafop 5%+Acifluorfen sodium 13% OD was observed in terms of weed control efficiency as compared to their tank mixes against mixed weed flora in peanut crop.
Trial 3:Phytotoxicity and Bioefficacy evaluation on Black gram crop
The field experiment was conducted on Black gram and experimental details as below:
Crop and Variety:Blackgram, LBG 787
Experimental design: Randomized block design
Replications: Four
No. of Treatments: Five
Plot size:40 sq. mt.
Application Time: 32 DAS (Days after sowing)
Observations: For phytotoxicity – 3, 7, 15 and 20 DAA (Days after Application)
For Bioefficacy- 15 and 30 DAA (Days after Application)
Water Volume: 375 liter per hectare
Application Equipment: Manually operated knap sack sprayer fitted with flat fat nozzle
Experiment Method: As per Example 1
Table 5 Phytotoxicity of novel formulations of Propaquizafop+Lactofen on Blackgram
Sr. No. Treatment Details Formulation (ml/ha) Active Ingredient (g/ha) Leaf Scorching (%)
3 DAA 7 DAA 15 DAA 20 DAA
1 Untreated Check - - 0 0 0 0
2 Propaquizafop 10% EC 600 ml 60.0 0.00 0.00 0.00 0.00
3 Lactofen 24% EC 750 ml 180.0 28.26 20.16 15.72 8.64
4 Propaquizafop 10% EC + Lactofen 24% EC (tank-mix) 600 ml + 750 ml 60 +180 26.82 17.14 9.52 5.38
5 Propaquizafop 5% + Lactofen15% OD (Oil Dispersion) 1200 ml 60 + 180 8.68 4.62 0.00 0.00

The novel formulation of Propaquizafop 5% + Lactofen 15% OD shows little leaf scorching on blackgram crop which recovers in 15 days after application and does not harm the growth.
Table 6 Weed control in Blackgram-Tank mix v/s Novel formulations of Propaquizafop 5% + Lactofen 15% OD
Sr.No. Treatment Details Formulation (ml/ha) Active Ingredient (g/ha) % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
1 Untreated Check - - 0 0
2 Propaquizafop 10% EC 600 ml 60.0 60.84 62.16
3 Lactofen 24% EC 750 ml 180.0 46.82 48.72
4 Propaquizafop 10% EC + Lactofen 24% EC (tank-mix) 600 ml + 750 ml 60 +180 76.82 78.84 79.17 80.60 0.97 0.98
5 Propaquizafop 5% + Lactofen 15% OD (Oil Dispersion) 1200 ml 60 + 180 97.92 98.42 79.17 80.60 1.24 1.22

Weed flora (Grasses – Echinochloa crus-galli, Satariaglauca, Broad leaf weeds – Trianthemaportulocastranum, Digeraarvensis, Boerhaviadiffusa, Phyllanthusniruri)
,CLAIMS:We claim;
[Claim 1]. A herbicidal composition comprising of Propaquizafop and co- herbicides, wherein co- herbicide is selected from Fomesafen, Lactofen, Acifluorfen, Bentazon, and Chloransulam methyl and one or more inactive excipients.
[Claim 2]. The herbicidal composition as claimed in claim 1 wherein the ratio of Propaquizafop to co-herbicide is 1:25 to 5:1.
[Claim 3]. The herbicidal composition as claimed in claim 1 or 2 wherein inactive excipients is selected from the group consisting of dispersant, adjuvant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents and buffering agent.
[Claim 4]. The herbicidal composition as claimed in claim 3 wherein adjuvant is Polyalkyleneoxide modified heptamethyltrisiloxane.
[Claim 5]. The herbicidal composition asclaimed in claim 1 to 4, wherein the formulation is in the form of Oil Dispersion (OD).
[Claim 6]. The herbicidal composition as claimed in any preceding claims, wherein the said composition is used for control insects or pastes in plants like Soybean (Glycine max), Peanut or Groundnut (Arachishypogaea), Mung bean or Green gram (Vignaradiata), Urad or Black gram (Vignamungo), Pegion pea or Red gram (Cajanuscajan), Bengal gram or Chickpea (Cicerarietinum), Rajma or French bean (Phaseolus vulgaris), Clusterbean (Cyamopsistetragonaloba), Cowpea (Vignaunguiculata), field peas, snap bean, alfalfa, lettuce, beans.

[Claim 7]. The herbicidal composition as claimed in claim 5, wherein the said composition is effective in controllingin controlling weeds like Monocotyledon weeds or grassy weeds of the genera such as Barnyard grass (Echinochloa spp.), Crabgrass (Digitaria spp.),Goosegrass (Eluesineindica),Millet grass (Panicumjavanicum), Foxtail (Setariaverticiliata), Bermuda grass (Cynodondactylon), Sorghum (Sorghum halepenses), Crow footgrass (Dactylocteniumaegyptium), Rottboelliacochinchinesis, Saccharumspontaneum, , Brachiariaarvensis.Dicotyledon weeds or broad leaved weeds of the genera such as Day flower (Commelinabenghalensis and Commelinasinensis), Pigweeds (Amaranthusviridis and Amaranthuslividis), Purslane (Portulacaoleracea), Morning glory (Ipomoea spp.), Nightshade (Solanum spp.), Spurge (Euphorbia geniculata and Euphorbia hirta), Ragweed (Ambroasia spp.), Small melon (Cucumis spp.), Starbur (Acanthospermum spp.), Cocklebur (Xanthium strumarium), Ground cherry (Physalis minima), Kotweed (Polygonum spp.), Thomapple (Datura spp.), Acalyphaindica, Wild jute (Corchorus), Digeraarvensis, Partheniumhysterophorus, Phyllanthusniruri, Alternantheraphiloxeroides, Trainthemaportulacastrum, Cyanotiscuculata, Cyanotisaxillaris, Lactucaruncinata, Boerhaviadiffusa, Hibiscus trionum,Loliumperenne L. ssp. multiflorum (Lam.) Husnot, Sidarhombifolia L., Anodacristata (L.) Schlecht.,Lamium spp. L, Cyperus di formis L., Croton sperrsifeorus, Nicandraphysalodes, Chenopodium album L