DESC:FIELD OF THE INVENTION:

The present invention relates to synergistic herbicidal composition comprising A) Bispyribac Sodium B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof with one or more inactive excipients. The present invention also relates to process for preparing the said composition and its use as herbicide.

BACKGROUND OF THE INVENTION

An herbicide is a pesticide used to kill unwanted plants. Selective herbicides kill certain targets weeds while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of the weed and are often based on plant hormones. Herbicides used to clear waste ground are nonselective and kill all plant material with which they come into contact. Herbicides are widely used in agriculture and in landscape turf management. They are applied in total vegetation control (TVC) programs for maintenance of highways and railroads. Smaller quantities are used in forestry, pasture systems, and management of areas set aside as wildlife habitat. The improper method of applying herbicide results in direct contact with field workers, inhalation of aerial sprays, food consumption and from contact with residual soil contamination. Some herbicides decompose rapidly in soils and other types have more persistent characteristics with longer environmental half-lives.

Bispyribac Sodium was first disclosed in EP021846. Chemically know as sodium;2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate and chemical structure of Bispyribac is as provided below;

Mode of action: selective, systemic action post-emergence herbicide, absorbed by foliage and roots.
Bispyribac sodium is a systemic herbicide that moves throughout the plant tissue and works by interfering with production of a plant enzyme necessary for growth, acetolactate synthase (ALS). It is used to control grasses, sedges and broad-leaved weeds, especially Echinochloa spp., in direct seeded rice. It is also used to stunt growth of weeds in non-crop situations. Bispyribac sodium is broken down by microbes and has a half-life (the time it takes for half of the active ingredient to degrade) of 42-115 days. The primary degradation product of bispyribac sodium is sodium 2-(4,6dimethoxypyrimidin-2-yl) oxy-6-(4-hydroxy-6- methoxy pyrimidin -2-yl) benzoate. Bispyribac sodium does not bind to soil, is moderately persistent and somewhat mobile through the soil. Testing indicates that the aquatic formulation of bispyribac sodium is non-toxic to fish and invertebrates. Bispyribac sodium is also non-toxic to both birds and mammals.
Fenoxaprop-p-ethyl is a selective herbicide with contact and systemic action, absorbed principally by the leaves, with translocation both acropetally and basipetally to the roots or rhizomes.

Fenoxaprop-p-ethyl is used for post-emergence controlling of annual and perennial grass weeds in potatoes, beans, soya beans, beets, vegetables, peanuts, flax, oilseed rape, and cotton; and (when applied with the herbicide safener mefenpyr-diethyl) and wild oats in wheat, rye, triticale and, depending on ratio, in some varieties of barley.

Cyhalofop butyl is a systemic post-emergence herbicide for the control of grassy weeds in direct seeded rice. Cyhalofop butyl can be used in paddy fields that are partially flooded or drained provided weeds are exposed to spray; thus provides flexibility for various water management practices. It has wide window of application, low potential for drift issues.
Pyrazosulfuron Ethyl is a new sulfonylurea herbicide for rice, being developed and launched in major rice producing countries.
In greenhouse studies, Pyrazosulfuron Ethyl demonstrated excellent herbicidal activity with both pre and post emergence applications. I75 values of Pyrazosulfuron Ethyl pre-emergence were below 10 g a. i./ha except for Echinochloa crus-galli. However, E. colona was much more sensitive. Selectivity of Pyrazosulfuron Ethyl between rice seedlings and Cyperus serotinus was sufficient, while that between rice seedling and E. crus-galli was marginal in water culture study. In field study, however Pyrazosulfuron Ethyl alone demonstrated a good control of Echinochloa crus-galli in china and other countries. It is necessary for Pyrazosulfuron ethyl to be combined with grass herbicide in dry seeded rice or in countries where they require higher performance and a wider application window.
Ethoxysulfuron is a post-emergent broad spectrum herbicide very effective for the control of sedges and broad leaf weeds in transplanted rice. Ethoxysulfuron as active ingredient which belongs to sulfonyl urea group of herbicides. When combined with grass herbicide like Ricestar as tankmix it can offer total weed control in rice.
Ethoxysulfuron is mainly taken up by the leaves and is translocated within the plant. After inhibition of plant growth, chlorotic patches develop and spread at first acropetally, then basipetally. The action of the product reaches its conclusion about 3-4 weeks after application with the death of the whole plant. Ethoxysulfuron acts by inhibition of the Enzyme acetolactate synthase (ALS).

Imazosulfuron is a selective herbicide providing both pre- and post-emergence control of sedges and broadleaf weeds. Imazosulfuron is registered for application to residential and commercial turfgrass, rice, tomatoes, and peppers.

Imazosulfuron is a systemic sulfonylurea (SU) herbicide that is absorbed both by roots and foliage and is translocated in the xylem and phloem. The mode of action is through the inhibition of the enzyme acetolactate synthase (ALS) leading to the blocking of the synthesis of the branch-chain amino acids such as valine, leucine, and isoleucine that are essential in the formation of new cells.

Propyrisulfuron, 1-(2-chloro-6-propylimidazo [1, 2-b] pyridazin-3-ylsulfonyl)-3-(4, 6-dimethoxypyrimidin-2-yl) urea is a novel sulfonylurea herbicide with a fused heterocyclic moiety, developed by Sumitomo Chemical Co., Ltd. Propyrisulfuron is used as a rice herbicide to control annual and perennial paddy weeds, including Echinochloa spp., sedges and broadleaf weeds. Propyrisulfuron controls weed biotypes that have developed resistance to the commercialized sulfonylurea herbicides. Propyrisulfuron shows safer profiles for human health and the environment. The granular formulation, suspension concentrate formulation and jumbo formulation (granules packed in water-soluble film) are available in Japan with the brand name of ZETA-ONE®

Azimsulfuron is a post-emergence herbicide for the control of annual and perennial broadleaf weeds and sedges and barnyard grass (Echinochloa spp). The product is suitable for use in all rice cultivation systems. Azimsulfuron is particularly suitable for foliar application: since uptake by roots is less efficient than update by leaves and shoots. The product is translocated in the xylem and phloem and weeds are killed within three weeks of application.
Tefuryltrione a triketon herbicide with a wide killing spectrum that is effective against sulfonylurea resistant weeds as well as annual and perennial weeds belonging to the Cyperus microiria Steud family. It is a new hydroxyl phenylpyruvate dioxygenase (HPPD) inhibitor induces plant death by inhibiting pigment synthesis in the target plants..
Penoxsulam is an acetolactate synthase inhibitor herbicide developed in the mid-2000s. This substance is designed to control existing broadleaf weeds and similar plants in lawns, rice fields and cereal crops. While penoxsulam is not effective against most grass species, it can be used to control a few specific weed grass species.
Penoxsulam was originally designed for use in rice fields and is capable of killing several grasses that prefer wet environments. These include barnyardgrass, young watergrass, Lolium ryegrasses, canarygrass species, annual blackgrass and wild buckwheat. According to Dow Agro Sciences, this herbicide also works on windgrass and other members of the Apera genus, which are frequent pests in wheat and other grain fields
Pyribenzoxim is a non-competetive inhibitor of ALS and the observed ALS inhibition data for rice and barnyard grass is similar suggesting that the basis for selectivity does not lie at the biochemical site of action. Transient chlorosis has been observed in crops 3-5 days after application but this is rapidly outgrown, it is proposed that the observed crop selectivity is due to rapid metabolism and perennial ryegrass.
Bentazon is a selective herbicide as it only damages plants unable to metabolize the chemical. It is considered safe for use on alfalfa, beans (with the exception of garbanzo beans, corn, peanuts, peas (with the exception of blackeyed peas, pepper, peppermint, rice, sorghum, soybeans and spearmint; as well as lawns and turf. Bentazon is usually applied aerially or through contact spraying on food crops to control the spread of weeds occurring amongst food crops. Herbicides containing bentazon should be kept away from high heat as it will release toxic sulfur and nitrogenfumes.
2,4-D (2,4-dichlorophenoxy) is a systemic phenoxy herbicide developed in the 1940s and still in use today. 2,4-D was the first widely used herbicide used to control broadleaf plants, and it has significantly contributed to modern weed control in agriculture.

2,4-D is chemically classified as a chlorophenoxy herbicide and is an odorless, crystalline powder that is colorless or white to yellow. 2,4-D is a strong oxidizer and is a non-combustible solid; however, it can be dissolved in flammable liquids. In addition to 2,4-D itself, there are eight salts and esters of 2,4-D. The most common form is the acid form, which is the subject of the majority of toxicity tests. 2,4-D has a chemical half-life in soil between seven and ten days, depending on temperature, moisture, sterility, nutrient composition, and oxygenation of the soil. 2,4-D is a post-emergence systemic herbicide used widely for selective control of broadleaf plants in a variety of food, forest, aquatic, and residential sites.

The effectiveness of herbicides depends, Inter alia, on the type of herbicide used, the application rate thereof, the composition, the harmful plants to be combated each time, the climatic and soil conditions, and the like. A further criterion is the duration of the action or the rate of degradation of the herbicide. Changes in the sensitivity of harmful plants to an active substance which may occur with relatively long use or in geographically restricted areas are also to be taken into account, if appropriate. Such changes are expressed as a more or less serious loss in activity and can only to a limited extent be compensated for by higher herbicide application rates.

Because of the multitude of possible influencing factors, there is virtually no individual active substance which combines in itself the properties desired for different requirements, in particular with regard to the harmful plant species and the climatic zones. In addition, there is the constant problem of achieving the effect with an ever lower herbicide application rate. A lower application rate reduces not only the amount of an active substance required for the application but generally also reduces the amounts of formulation auxiliaries necessary. Both reduce the economic cost and improve the ecological compatibility of the herbicide treatment.

One method frequently used for improving the application profile of a herbicide consists in combining the active substance of one or more other active substances which contribute the additional properties desired. However, the combined use of several active substances not infrequently results in phenomena of physical and biological incompatibility, e.g. lack of stability of a combined formulation, decomposition of an active substance or antagonism of the active substances. On the other hand, what is desired are combinations of active substances with a favorable activity profile, high stability and the greatest possible synergistically strengthened activity which makes possible a reduction in the application rate in comparison with individual application of the active substances to be combined.

Indian patent application 201717023476 describes Methods for controlling weeds using synergistic compositions containing penoxsulam, triclopyr, and bispyribac, especially rice, sugarcane, cereal and grain crops, pastures, rangelands, industrial vegetation management (rVM), aquatics and turf, as well as protecting crops from herbicidal injury caused by any of the individual components. These methods provide improved post-emergence herbicidal weed control and reduce herbicidal injury by concomitant application of the mixture.

Indian patent application 201641006356 discloses broad spectrum synergistic herbicidal composition comprising formula (a) Pyrazosulfuron ethyl (b) Bispyribac sodium, (c) at least one wetting agent with 0.5 to 5 % of total mass of the composition, (d) at least one dispersing agent with 0.5 to 6 % of the total mass of the composition, (e) at least one De-foamer with 0.1 to 1.0 % of the mass composition (f) at least one filler with 10 to 55% of the mass of the composition wherein Pyrazosulfuron ethyl andBispyribac sodium are present in a weight ratio ranging from (5:4 to 1:5). The herbicidal composition of the present invention is useful for the effective control of a broad range of weeds in economically important rice crops. The process of making composition also disclosed.

Indian patent application 1383/DELNP/2015 synergistic herbicidal compositions containing (a) a compound of formula (I): 4-amino-3-chloro-5- fluoro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylic acid or a derivative thereof, or an agriculturally acceptable salt or ester thereof and (b) dimethoxy- pyrimidine acids, including but not limited to bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac-methyl and pyrimisulfan provide synergistic weed control of undesirable vegetation e.g., in direct seeded, water-seeded, and transplanted rice, cereals, wheat, barley, oats, rye, sorghum, com or maize, sugarcane, sunflower, oilseed rape, canola, sugar beet, soybean, cotton, pineapple, vegetables, pastures, grasslands, rangelands, fallowland, turf, tree and vine orchards, aquatics, plantation crops, industrial vegetation management (rVM) or rights of way (ROW).

Indian patent application 201727025976 describes a one shot herbicide composition comprising at least one herbicidal active ingredient selected from Groups 1 and/or Group 2 and at least one polymer where the composition is formulated into a granule or sprayable form wherein Group 1 consists of bispyribac sodium, cyhalofop butyl, metamifop, pyribenzoxim, azimsulfuron, flucetosulfuron, metazosulfuron, pyrimisulfan, profoxydimpyriminobac methyl, mefenacet, benzobicyclon, clomazone, fenoxaprop P ethyl, quinclorac and propyrisulfuron; Group 2 consists of members of the protoporphyrinogen oxidase inhibitor group (PPO inhibitor herbicides) and the branched chain amino acid inhibitor group (ALS or AHAS inhibitor herbicides) other than those listed in Group 1; and one or more of the at least one herbicidal active ingredient is/are dispersed in the at least one polymer.

Indian patent application 7411/CHENP/2009 describes Synergistic crop-tolerated combinations of herbicides from the benzoylcyclohexane-dione group for application in rice growing Herbicidal combinations comprising bensulfuron-methyl, benzobicyclon, bromobutide, cyhalofop-butyl, ethoxysulfuron, fenoxaprop-P-ethyl, fentrazamide, pyrazolynate, pyrimisulfan, sulcotrione, tefuryltrione, tembotrione and, if appropriate, isoxadifen-ethyl are described. These combinations exhibit an effect which is superior to that of the herbicides used individually.

However still there is a need for a synergistic herbicidal composition which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.

Inventors of the present invention have surprisingly found that the synergistic herbicidal composition comprising A) Bispyribac Sodium B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof with one or more inactive excipients described herein in can provide solution to the above mentioned problems.

SUMMARY OF THE INVENTION

It is an aspect of the present invention is to provide, with a view to effective resistance management and effective control of weeds especially grassy weeds, at application rates which are as low as possible, compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful weeds and a broadened activity spectrum, in particular for certain indications.

We have accordingly found that this object is achieved by synergistic herbicidal composition comprising A) Bispyribac Sodium B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof with one or more inactive excipients.

Accordingly, in a main aspect of the present invention provides a synergistic herbicidal composition comprising A) Bispyribac Sodium B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof with one or more inactive excipients.

Accordingly, in a second aspect, the present invention provides a method of preparing the synergistic herbicidal composition comprising A) Bispyribac Sodium B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof with one or more inactive excipients.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides solution to all the problems mentioned above by providing the synergistic herbicidal composition.

The present invention provides a synergistic herbicidal composition comprising A) Bispyribac Sodium B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof with one or more inactive excipients.

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

The term “formulation” and “composition” as used herein conveys the same meaning and can be used interchangeably.

As used herein, the term "synergistic" means a combination of components wherein the activity of the combination is greater than the sum of the individual activities of each component of the combination.

The term herbicide, as used herein, means an active ingredient that kills, controls or otherwise adversely modifies the growth of plants. As used herein, a herbicidally effective or vegetation controlling amount is an amount of active ingredient that causes a "herbicidal effect," i.e., an adversely modifying effect such as a deviation from natural development, killing, regulation, desiccation and retardation.

The formulation or composition of the present invention can be in various physical forms, for example in the form of a dustable powder (DP), a gel, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG), a water-dispersible tablet (WT), an emulsifiable concentrate (EC), a micro- emulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable ( a spreading oil (SO), an aqueous dispersion ( aqueous suspension concentrate (SC)), an oily dispersion (OD), a suspo-emulsion (SE), a capsule suspension (CS), a soluble liquid (SL), a water-soluble concentrate (with water or a water-miscible organic solvent as carrier), ZC (Mixed formulation of CS and SC), ZE (Mixed formulation of CS and SE), ZW (Mixed formulation of CS and EW).

In a preferred embodiment, the composition of present invention is sleeted from SC (Suspension Concentrate), SL (soluble liquid), CS (Capsule Suspension), EC (Emulsifiable Concentrate), ZC (Mixed formulation of CS and SC), ZE (Mixed formulation of CS and SE), ZW (Mixed formulation of CS and EW), WG (water-dispersible granules) and WP (wettable powder)

As per one embodiment, the synergistic herbicidal composition comprising A) Bispyribac Sodium B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof with one or more inactive excipients, wherein active ingredients are present in concentration as described below;

Compound A Compound B Compound C

Active ingredients Bispyribac Sodium Fenoxaprop-P-Ethyl Pyrazosulfuron Ethyl
Cyhalofop butyl Ethoxysulfuron
Imazosulfuron
Propyrisulfuron..
Azimsulfuron
Tefuryltrione
Penoxsulam
Pyribenzoxim
Bentazon
2,4-D (different salt)
Concentration 0.1-10% 0.1-20% 0.1-70%

In another embodiment of the present invention the synergistic herbicidal composition comprising
A) Bispyribac Sodium;
B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof;
C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof;
with one or more inactive excipients effective for controlling or killing of resistant and tough to control weeds especially grassy weeds.

In another embodiment of the present invention the synergistic herbicidal composition comprising
A) Bispyribac Sodium;
B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof;
C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof;
D) Optionally at least one or more safeners; and with one or more inactive excipients effective for controlling or killing of resistant and tough to control weeds especially grassy weeds.

As per one embodiment, the active herbicidal compound as mentioned above to be used in the composition of present invention can be in the form of base or any salts form known in the art.

Furthermore, in some embodiments, the combination of A) Bispyribac Sodium B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof with one or more inactive excipients, exhibits synergism, i.e., the herbicidal active ingredients are more effective in combination than when applied individually. The Herbicide Handbook of the Weed Science Society of America, Ninth Edition, 2007, p. 429 notes that synergism is “an interaction of two or more factors such that the effect when combined is greater than the predicted effect based on the response of each factor applied separately.” In certain embodiments, the compositions exhibit synergy as determined by the Colby's equation. Colby, S. R. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 1967, 15, 20-22.

Herbicidal activity (control of undesirable vegetation) is exhibited by the compositions when they are applied directly to the plant or to the locus of the plant at any stage of growth. The effect observed depends upon the plant species to be controlled, the stage of growth of the plant, the application parameters of dilution and spray drop size, the particle size of solid components, the environmental conditions at the time of use, the specific compound employed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of chemical applied. These and other factors can be adjusted to promote non-selective or selective herbicidal action. In some embodiments, the compositions described herein are applied to relatively immature undesirable vegetation to achieve the maximum control of weeds.

In some embodiments, the compositions and methods provided herein are utilized to control weeds in cereal crops, including but not limited to rice, wheat, barley, tritcale, oats, rye, sorghum, corn/maize, and also in cereal crops. Weeds that may be controlled by this method include; Echinochloa crus-galli, Leptochloa chinensis, Ischaemum rugosum, Sphenoclea zeylanica, Cyperus difformis, Cyperus iria, Cyperus seotinus, Fimbristylis, Monochoria vaginalis, Echinochloa colonum, Sphenoclea, Eleocharis, Marsilea, Saggitaria, Scirpus maritimus, Scirpus mucronatus and Sesbania.

In one embodiment of the present invention, the Herbicidal composition of present invention controls weeds listed below;

The synergistic composition of present invention is effective for control of Aeschynomene aspera, Aeschynomene indica, Ageratum conyzoides, Alternanthera sessilis, Alternanthera philoxeroides, Amaranthus spinosus, Amaranthus viridis, Ammania baccifera, Cynodon dactylon, Dactyloctenium aegyptium, Digitaria ciliaris, Digitaria setigera, Ischaemum rugosum, Echinochloa colona, Echinochloa crus-galli, Echinochloa glabrescens, Echinochloa crus-pavonis, Echinochloa esculenta, Echinochloa frumentacea, Echinochloa muricata, Echinochloa oryzoides, Echinochloa paludigena, Eleocharis kuruguwai, Laptochloa chinensis, Eleusine indica, Eclipta alba, Eclipta prostate, Imperata cylindrical, Leersia hexandra, Leptochloa chinensis, Oryza sativa, Panicum repens, Paspalum distichum, Paspalum scrobiculatum, Rottboellia cochinchinensis, Setaria glauca, Bolboschoenus maritimus, Bergia capensis, Commelina benghalensis, Commelina diffusa, Cyanotis axillaris, Eclipta alba, Eclipta prostrate, Eichhornia crassipes, Ipomoea aquatic, Ludwigia adscendens, Ludwigia hyssopifolia, Ludwigia octovalvis, Ludwigia parviflora, Marsilea minuta, Marsilea quadrifoliata, Mimosa diplotricha, Monochoria vaginalis, Pistia stratiotes, Polygonum hydropiper, Portulaca oleracea, Sagittaria milliacea, Sagittaria sagittifolia, Sphenoclea zeylanica, Trianthema portulacastrum, Typha spp., Isachne globosa, Paspalum distichum, Cyperus difformis, Cyperus haspen, Cyperus iria, Cyperus rotundus, Fimbristylis dichotoma, Fimbristylis miliacea, Scirpus juncoides, Scirpus nipponicus, Scirpus planiculmis, Scirpur royelei, Scirpus juncoides. The composition of present invention especially effective for control of Dactyloctenium aegyptium, Digitaria ciliaris, Ischaemum rugosum and Laptochloa chinensis, Oryza sativa (Red rice)

The synergistic herbicidal composition of present invention is to be used for Paddy or Rice (Oryza sativa L.) including Indica, Japonica and Javanica race. GMO (Genetically Modified) Paddy, Sugarcane, Maize, Wheat and Industrial land and non-cropped area.

Method of application:
As per one embodiment, the synergistic herbicidal composition of present invention is to be applied as Post emergence application: Spray over the crop and weeds with manual or power operated sprayer. It can be applied in transplanted paddy, direct wet sown rice, dry seeded rice, pre-germinated direct sown rice, drilled rice etc.

Application Time:
As per one embodiment, the synergistic herbicidal composition of present invention can be applied on actively growing weeds from 2 leaf stage to fully grown weeds. It can be applied in nursery as well as main field after sowing or transplanting.

One or more inactive excipient is selected from including but not limited to safeners, 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.

Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or stearic barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersants are sodium lignosulphonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersants used herein include but not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.

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

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

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

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

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

Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspo-emulsions 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, bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof. Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.

The quick coating agent can be a conventionally available sticker, for example polyesters, polyamides, poly- carbonates, polyurea and polyurethanes, acrylate polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, 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 invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch esteraliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.

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

The safeners for the formulation of the present invention are preferably selected from the group consisting of mefenpyr ester or fenchlorazole, derivatives of cloquintocet, such as cloquintocet mexyl), daimuron, dichlormid, dicyclonon, dimepiperate, fenclorim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (NA), or agriculturally acceptable salts, esters, or mixtures thereof.

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

The SC formulation can be prepared by below described method;

STEP-I: Adding anti-microbial agent and gum in water under continuous stirring followed by slow addition. Continuing stirring until homogeneous dispersion is formed.

STEP-II: Mixing anti-freezing agent, dispersant, wetting agent, anti-microbial agent and anti-foaming agent in water for 30 minute until homogeneous solution is formed. Finally add A) Bispyribac Sodium B) at least one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof C) at least one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof which are standard in agriculture or mixture thereof is added slowly under continuous stirring at 30 minute till homogeneous dispersion is obtained. Milling the slurry through bead mill until required particle size is achieved.

Step-III: Adding rest of water, anti-foaming agent and gum solution under continuous stirring to get desired viscosity of the suspension. Continue stirring for about 4 hr. to obtain homogeneous formulation.

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

EXAMPLES

Example 1: Suspension concentrate (SC) formulation of Bispyribac sodium (5%), Fenoxaprop-P-Ethyl (12%) and Pyrazosulfuron Ethyl (5%).

Chemical composition % (w/w)
Bispyribac sodium a.i. 5.00
Fenoxaprop-P-Ethyl a.i. 12.00
Pyrazosulfuron Ethyl a.i. 5.00
Ethoxylated fatty alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated napthalene sulfonate, sodium salt 0.50
Precipitated Silica 0.50
Polydimethyl siloxane 0.30
1,2-benzisothiazol-3-one 0.05
Glycol 5.00
Xanthan gum 0.15
Polyalkoxylated butyl ether 1.00
D.M. Water q.s.
Total 100.00

Procedure:

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

Example 2: Suspension concentrate (SC) formulation of Bispyribac sodium (1.5%), Fenoxaprop-P-Ethyl (3.6%) and 2,4-D Amine salt (30%).

Chemical composition % (w/w)
Bispyribac sodium a.i. 1.50
Fenoxaprop-P-Ethyl a.i. 3.60
2,4-D Amine salt a.i. 30.00
Ethoxylated fatty alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated napthalene sulfonate, sodium salt 0.50
Precipitated Silica 0.50
Polydimethyl siloxane 0.30
1,2-benzisothiazol-3-one 0.05
Glycol 5.00
Xanthan gum 0.15
Polyalkoxylated butyl ether 1.00
D.M. Water q.s.
Total 100.00

Procedure: as per Example 1

Example 3: SL (Soluble Liquid) formulation of Bispyribac sodium (1.5%), Fenoxaprop-P-Ethyl (3.6%) and 2,4-D Amine salt (30%)

Chemical composition % (w/w)
Bispyribac sodium a.i. 1.50
Fenoxaprop-P-Ethyl a.i. 3.60
2,4-D Amine salt a.i. 30.00
Aromatic Hydrocarbon 5.00
Polyalkoxylated butyl ether 2.00
Polyethelene Glycol 10.00
Trisiloxane Ethoxylate 2.00
Silicon emulsion antifoam 0.50
Water q.s.
TOTAL 100.00

Procedure: as per Example 1

Example 4: SC (suspension concentrate) of Bispyribac sodium (5%), Cyhalofop Butyl (15%) and Pyrazosulfuron Ethyl (5%)

Chemical composition % (w/w)
Bispyribac sodium a.i. 5.00
Cyhalofop Butyl a.i. 15.00
Pyrazosulfuron Ethyl a.i. 5.00
Ethoxylated fatty alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated napthalene sulfonate, sodium salt 0.50
Precipitated Silica 0.50
Polydimethyl siloxane 0.30
1,2-benzisothiazol-3-one 0.05
Glycol 5.00
Xanthan gum 0.15
Polyalkoxylated butyl ether 1.00
D.M. Water q.s.
Total 100.00

Procedure: as per Example 1

Example 5: SC (suspension concentrate) of Bispyribac sodium (1.5%), Cyhalofop Butyl (5%) and 2,4-D Amine salt (30%)

Chemical composition % (w/w)
Bispyribac sodium a.i. 1.50
Cyhalofop Butyl a.i. 5.00
2,4-D Amine salt a.i. 30.00
Ethoxylated fatty alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated napthalene sulfonate, sodium salt 0.50
Precipitated Silica 0.50
Polydimethyl siloxane 0.30
1,2-benzisothiazol-3-one 0.05
Glycol 5.00
Xanthan gum 0.15
Polyalkoxylated butyl ether 1.00
D.M. Water q.s.
Total 100.00

Procedure: as per Example 1

Example 6: Process of preparation of SL (Soluble Liquid) of Bispyribac sodium (1.5%), Cyhalofop Butyl (5%) and 2,4-D Amine salt (30%)

Chemical composition % (w/w)
Bispyribac sodium a.i. 1.50
Cyhalofop Butyl a.i. 5.00
2,4-D Amine salt a.i. 30.00
Aromatic Hydrocarbon 5.00
Polyalkoxylated butyl ether 2.00
Polyethelene Glycol 10.00
Trisiloxane Ethoxylate 2.00
Silicon emulsion antifoam 0.50
Water q.s.
Total 100.00

Example 7 to 28
Most Preferred formulations

Sr No a.i.1 a.i.2 a.i.3 active ingredients in % Formulation Strength (%) Formulation Type Application Rate (g per hectare) g.a.i per hectare
a.i.1 a.i.2 a.i.3 a.i.1 a.i.2 a.i.3
7 Bispyribac sodium Fenoxaprop-P-Ethyl Pyrazosulfuron Ethyl 5 12 5 22 SC 375 18.75 45.00 18.75
8 Bispyribac sodium Fenoxaprop-P-Ethyl Ethoxysulfuron 5 12 4 21 SC 375 18.75 45.00 15.00
9 Bispyribac sodium Fenoxaprop-P-Ethyl Imazosulfuron 5 12 15 32 SC 375 18.75 45.00 56.25
10 Bispyribac sodium Fenoxaprop-P-Ethyl Propyrisulfuron 5 12 15 32 SC 375 18.75 45.00 56.25
11 Bispyribac sodium Fenoxaprop-P-Ethyl Azimsulfuron 5 12 15 32 SC 375 18.75 45.00 56.25
12 Bispyribac sodium Fenoxaprop-P-Ethyl Tefuryltrione 1.875 4.5 25 31.375 SC 1000 18.75 45.00 250.00
13 Bispyribac sodium Fenoxaprop-P-Ethyl Penoxsulam 5 12 6 23 SC 375 18.75 45.00 22.50
14 Bispyribac sodium Fenoxaprop-P-Ethyl Pyribenzoxim 5 12 10 27 SC 375 18.75 45.00 37.50
15 Bispyribac sodium Fenoxaprop-P-Ethyl Bentazon 1.25 3 30 34.25 SC 1500 18.75 45.00 450.00
16 Bispyribac sodium Fenoxaprop-P-Ethyl 2,4-D Amine Salt 1.5 3.6 30 35.1 SC 1250 18.75 45.00 375.00
17 Bispyribac sodium Fenoxaprop-P-Ethyl 2,4-D Amine Salt 1.5 3.6 30 35.1 SL 1250 18.75 45.00 375.00
18 Bispyribac sodium Cyhalofop butyl Pyrazosulfuron Ethyl 5 15 5 25 SC 400 20.00 60.00 20.00
19 Bispyribac sodium Cyhalofop butyl Ethoxysulfuron 5 15 4 24 SC 400 20.00 60.00 16.00
20 Bispyribac sodium Cyhalofop butyl Imazosulfuron 5 15 12.5 32.5 SC 400 20.00 60.00 50.00
21 Bispyribac sodium Cyhalofop butyl Propyrisulfuron 5 15 12.5 32.5 SC 400 20.00 60.00 50.00
22 Bispyribac sodium Cyhalofop butyl Azimsulfuron 5 15 12.5 32.5 SC 400 20.00 60.00 50.00
23 Bispyribac sodium Cyhalofop butyl Tefuryltrione 2 6 25 33 SC 1000 20.00 60.00 250.00
24 Bispyribac sodium Cyhalofop butyl Penoxsulam 5 15 5 25 SC 400 20.00 60.00 20.00
25 Bispyribac sodium Cyhalofop butyl Pyribenzoxim 5 15 10 30 SC 400 20.00 60.00 40.00
26 Bispyribac sodium Cyhalofop butyl Bentazon 1.25 4 30 35.25 SC 1500 18.75 60.00 450.00
27 Bispyribac sodium Cyhalofop butyl 2,4-D Amine Salt 1.5 5 30 36.5 SC 1250 18.75 62.50 375.00
28 Bispyribac sodium Cyhalofop butyl 2,4-D Amine Salt 1.5 5 30 36.5 SL 1250 18.75 62.50 375.00

Stability studies:

Stability studies on all of the above formulations were carried out as per standards set forth and the same has been found to be stable.

Biological Examples:
Field experiments of inventive mixtures of bispyribac sodium+fenoxaprop-p-ethyl+ pyrazosulfuron ethyl, bispyribac sodium+fenoxaprop-p-ethyl+2,4-D amine salt, bispyribac sodium+cyhalofop butyl+pyrazosulfuron ethyl were carried on paddy crop to evaluate their phyto toxicity and bioefficacy against different weed flora existing in paddy field.

Example 29 Bioefficacy and phytotoxicity to direct seed paddy (Oryza sativa L.)
The field experiment was conducted on paddy and experimental details as below:
Crop & Variety: Paddy, MTU 1010 (direct seeded paddy)
Experimental design : Randomized block design (R.B.D)
Replications : Three
No. of Treatments : Twelve (12)
Plot size : 30 sq. mt.
Application Time : 15 DAS (Days after sowing)
Observations : at 5 and 10 DAA for phytotoxicity and 15 and 30 DAA (Days after Application) for bioefficacy against weeds
Spray Volume : 375 liter water per hectare
Application Equipment : Manually operated knap sack sprayer fitted with flat fat 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 of bispyribac sodium+ fenoxaprop-p-ethyl+ pyrazosulfuron ethyl, bispyribac sodium+fenoxaprop-P-ethyl+2,4-D amine salt. The trial was laid out in Randomized Block Design (RBD) with twelve treatments including untreated check (UTC), replicated three times. For each treatment plot size of 30 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 375 l/h for spraying. The Untreated check plot was sprayed with water alone. Observations on phytotoxicity viz., yellowing, leaf tip burning and stunting was recorded at 5 and 10 days after spraying, by adopting 0-10 rating scale as below:

0= No phytotoxicity, 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% and 10=91-100% phytotoxicity

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

Table 1: Phytotoxicity on direct seeded paddy
Treatment Details Formulation (ml or g per h) Active Ingredient (g/h) Yellowing (%) Leaf tip burning (%) Stunting (%)
5 DAA 10 DAA 5 DAA 10 DAA 10 DAA 20 DAA
Bispyribac sodium 5%+Fenoxaprop-P-Ethyl 12%+Pyrazosulfuron Ethyl 5% SC 375 18.75+45+18.75 5.0 0.0 0.0 0.0 0.0 0.0
Bispyribac sodium 1.5%+Fenoxaprop-P-Ethyl 3.6%+2,4-D Amine salt 30% SC 1250 18.75+45+375 5.0 0.0 5.0 0.0 0.0 0.0
Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix) 187.5+652 18.75+45 15.0 10.0 10.0 5.0 10.0 10.0
Bispyribac sodium 10%SC+ Pyrazosulfuron Ethyl 10% WP (tank mix) 187.5+187.5 18.75+18.75 0.0 0.0 0.0 0.0 0.0 0.0
Bispyribac sodium 10% SC+ 2,4-D Amine salt 58% SL (tank mix) 187.5+647 18.75+375 10.0 5.0 10.0 5.0 10.0 5.0
Fenoxaprop-P-Ethyl 6.9% EC+ Pyrazosulfuron Ethyl 10% WP (tank mix) 652+187.5 45+18.75 15.0 10.0 10.0 5.0 5.0 5.0
Fenoxaprop-P-Ethyl 6.9% EC+ 2,4-D Amine salt 58% SL (tank mix) 652+647 45+375 15.0 10.0 10.0 5.0 10.0 10.0
Bispyribac sodium 10% SC 187.5 18.75 0.0 0.0 0.0 0.0 0.0 0.0
Fenoxaprop-P-Ethyl 6.9% (6.7% w/w) EC 652 45 10.0 5.0 10.0 10.0 15.0 10.0
Pyrazosulfuron Ethyl 10% WP 187.5 18.75 0.0 0.0 0.0 0.0 0.0 0.0
2,4-D Amine Salt 58% SL 647.0 375.00 15.0 10.0 10.0 5.0 5.0 5.0
Unweeded control 0 0 0.0 0.0 0.0 0.0 0.0 0.0
ml- milli liter, g- gram, h-hectare, UTC- Untreated Check, DAS- Days After Sowing, SC- Suspension Concentrate, EC- Emulsifiable Concentrate, WP-Wettable Powder

The results of the field trial presented in table 1 indicates that the inventive synergistic mixtures of bispyribac sodium+fenoxaprop-p-ethyl+pyrazosulfuron ethyl, bispyribac sodium+ fenoxaprop-P-ethyl+ 2,4-D amine salt shows marginal yellowing (i.e. up to 5%) on 5th days after application which was completely recovered on 10th day without affecting normal plant growth. The inventive synergistic mixture of bispyribac sodium+fenoxaprop-p-ethyl+ pyrazosulfuron ethyl, bispyribac sodium+fenoxaprop-p-ethyl+2,4-D amine salt were found safe to the paddy crop.

Bioefficacy evaluation
A synergistic effect exists wherever the action of a combination of active ingredient is greater than the sum of the action of each of the components alone. Therefore a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater herbicidal activity than the sum of the herbicidal activities of the individual components.
In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated herein by reference in its entirety. The action expected for a given combination of two active components can be calculated as follows:

The synergistic herbicidal action of the inventive mixtures can be demonstrated by the experiments below.
Species wise weed count recorded at 15 and 30 DAA (Days After Application) by using 0.25 m2 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.

% Weed Control =

Mean weed count in untreated plot – Mean weed control in treated plot
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 2: Bioefficacy against mixed weed flora in direct seeded paddy
Treatment Details Formulation (ml or g per h) Active Ingredient (g/h) % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
Bispyribac sodium 5%+Fenoxaprop-P-Ethyl 12%+Pyrazosulfuron Ethyl 5% SC 375 18.75+45+18.75 98.4 96.2 87.59 81.21 1.12 1.18
Bispyribac sodium 1.5%+Fenoxaprop-P-Ethyl 3.6%+2,4-D Amine salt 30% SC 1250 18.75+45+375 97.9 95.7 87.36 81.78 1.12 1.17
Bispyribac sodium 10% SC+ Fenoxaprop-P-Ethyl 6.9% EC (tank mix) 187.5+652 18.75+45 71.5 63.6 74.37 68.27 0.96 0.93
Bispyribac sodium 10%SC+ Pyrazosulfuron Ethyl 10% WP (tank mix) 187.5+187.5 18.75+18.75 69.8 65.4 79.04 69.45 0.88 0.94
Bispyribac sodium 10% SC+ 2,4-D Amine salt 58% SL (tank mix) 187.5+647 18.75+375 68.4 58.3 78.65 70.38 0.87 0.83
Fenoxaprop-P-Ethyl 6.9% EC+ Pyrazosulfuron Ethyl 10% WP (tank mix) 652+187.5 45+18.75 68.3 58.2 71.35 63.59 0.96 0.92
Fenoxaprop-P-Ethyl 6.9% EC+ 2,4-D Amine salt 58% SL (tank mix) 652+647 45+375 67.8 55.2 70.81 64.70 0.96 0.85
Bispyribac Sodium 10% SC 187.5 18.75 56.7 48.4
Fenoxaprop-P-Ethyl 6.9% (6.7% w/w) EC 652 45 40.8 38.5
Pyrazosulfuron Ethyl 10% WP 187.5 18.75 51.6 40.8
2,4-D Amine Salt 58% SL 647.0 375.00 50.7 42.6
Unweeded control 0 0 0.0 0.0
ml- milli liter, g- gram, h-hectare, UTC- Untreated Check, DAS- Days After Sowing, SC- Suspension Concentrate, EC- Emulsifiable Concentrate, WP-Wettable Powder

The field trials results presented in table 2 shows that inventive synergistic combination of bispyribac sodium+fenoxaprop-p-ethyl+pyrazosulfuron ethyl and bispyribac sodium+fenoxaprop-p-ethyl+2,4-D amine salt shows synergistic effect in terms of total weed control i.e. grasses, broadleaf weeds and sedges, in comparison to tank mix combinations of bispyribac sodim+fenoxaprop-p-ethyl, bispribac sodium+pyrazosulfuron ethyl, bispyribac sodium+2,4-D amine salt, fenoxaprop-p-ethyl+2,4-D amine salt and fenoxaprop-pethyl+pyrazosulfuron ethyl.

Experiment 30 Bioefficacy and Phytotoxicity to transplanted paddy (Oryza sativa)
Crop & Variety : Paddy, Sona Masuri
Experimental design : Randomized block design (R.B.D)
Replications : Three
No. of Treatments : Eight
Plot size : 50 sq. mt.
Application Time : 24 DAS (Days after transplanting)
Observations : 15 and 30 DAA (Days after Application)
Spray Volume : 400 liter water per hectare
Application Equipment : Manually operated knap sack sprayer fitted with flat fat nozzle

Experimental Methodology : Same as in Example 1

Table 3: Phytotoxicity on transplanted paddy
Treatment Details Formulation (ml or g per h) Active Ingredient (g/h) Yellowing (%) Leaf tip burning (%) Stunting (%)
5 DAA 10 DAA 5 DAA 10 DAA 10 DAA 20 DAA
Bispyribac sodium 5%+Cyhalofop butyl 15%+Pyrazosulfuron Ethyl 5% SC 200+600+200 20+60+20 0.0 0.0 0.0 0.0 0.0 0.0
Bispyribac sodium 10% SC+ Cyhalofop butyl 10% EC (tank mix) 200+600 20+60 10.0 5.0 10.0 5.0 10.0 5.0
Bispyribac sodium 10%SC+ Pyrazosulfuron Ethyl 10% WP (tank mix) 200+200 20+20 0.0 0.0 0.0 0.0 0.0 0.0
Cyhalofop butyl 10% EC+ Pyrazosulfuron Ethyl 10% WP (tank mix) 600+200 60+20 10.0 5.0 10.0 5.0 10.0 5.0
Bispyribac sodium 10% SC 200 20 0.0 0.0 0.0 0.0 0.0 0.0
Cyhalofop butyl 10% EC 600 60 10.0 5.0 10.0 5.0 10.0 5.0
Pyrazosulfuron Ethyl 10% WP 200 20 0.0 0.0 0.0 0.0 0.0 0.0
Unweeded control 0 0 0.0 0.0 0.0 0.0 0.0 0.0
ml- milli liter, g- gram, h-hectare, UTC- Untreated Check, DAS- Days After Sowing, SC- Suspension Concentrate, EC- Emulsifiable Concentrate, WP-Wettable Powder

The field trial results shows that combination of bispyribac sodium+cyhalofop butyl+pyrazosulfuron ethyl did not shows any kind of Phytotoxicity to transplanted paddy.

Table 4: Bioefficacy against mixed weed flora in transplanted paddy
Treatment Details Formulation (ml or g per h) Active Ingredient (g/h) % Weed Control Observed % Weed Control Expected Colby Ratio o/e
15 DAA 30 DAA 15 DAA 30 DAA 15 DAA 30 DAA
Bispyribac sodium 5%+Cyhalofop butyl 15%+Pyrazosulfuron Ethyl 5% SC 200+600+200 20+60+20 99.2 98.2 90.12 82.97 1.10 1.18
Bispyribac sodium 10% SC+ Cyhalofop butyl 10% EC (tank mix) 200+600 20+60 74.2 68.6 81.43 72.45 0.91 0.95
Bispyribac sodium 10%SC+ Pyrazosulfuron Ethyl 10% WP (tank mix) 200+200 20+20 70.2 64.8 77.44 68.11 0.91 0.95
Cyhalofop butyl 10% EC+ Pyrazosulfuron Ethyl 10% WP (tank mix) 600+200 60+20 66.4 60.2 76.70 67.00 0.87 0.90
Bispyribac sodium 10% SC 200 20 57.6 48.4
Cyhalofop butyl 10% EC 600 60 56.2 46.6
Pyrazosulfuron Ethyl 10% WP 200 20 46.8 38.2
Unweeded control 0 0 0.0 0.0
ml- milli liter, g- gram, h-hectare, UTC- Untreated Check, DAS- Days After Sowing, SC- Suspension Concentrate, EC- Emulsifiable Concentrate, WP-Wettable Powder

The field trials results presented in table 4 shows that inventive synergistic combination of bispyribac sodium+cyhalofop butyl+pyrazosulfuron ethyl shows synergistic effect in terms of total weed control i.e. grasses, broadleaf weeds and sedges, in comparison to tank mix combinations of bispyribac sodim+cyhalofop butyl, bispyribac sodium+pyrazosulfuron ethyl and cyhalofop butyl+pyrazosulfuron ethyl.
,CLAIMS:CLAIMS
We claim;
[CLAIM 1]. An synergistic herbicidal composition comprising
A) Bispyribac Sodium;
B) one herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl and salts thereof;
C) further one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof; and
(D) Optionally at least one or more safeners and one or more inactive excipients.

[CLAIM 2]. The synergistic composition as claimed in claim 1 wherein the component (A) Bispyribac Sodium is in ratio of 0.1 to 10%, component (B) herbicide selected from Fenoxaprop-P-Ethyl and Cyhalofop butyl is in ratio of 0.1 to 20% and component (C) further one more herbicide selected from Pyrazosulfuron Ethyl, Ethoxysulfuron, Imazosulfuron, Propyrisulfuron, Azimsulfuron, Tefuryltrione, Penoxsulam, Pyribenzoxim, Bentazon, 2,4-D and salts thereof is in ratio of 0.1 to 70%.

[CLAIM 3]. The synergistic composition as claimed in claim 1-2, wherein inactive excipients are selected from the group consisting of safeners, dispersant, 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 synergistic composition as claimed in claim 1-3 wherein safeners for the formulation of the present invention are preferably selected from the group consisting of mefenpyr ester or fenchlorazole, derivatives of cloquintocet, such as cloquintocet mexyl), daimuron, dichlormid, dicyclonon, dimepiperate, fenclorim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (NA)

[CLAIM 5]. The synergistic composition as claimed in claim 1-3, wherein the formulations comprises of Suspension Concentrate (SC) or Soluble Liquid (SL).

[CLAIM 6]. The formulation comprising the synergistic composition as claimed in claim 4, wherein the SC (Suspension Concentrate) formulation comprises:
a) Ethoxylated fatty alcohol;
b) Acrylic graft copolymer;
c) Alkylated napthalene sulfonate, sodium salt;
d) Precipitated Silica;
e) Polydimethyl siloxane;
f) 1,2-benzisothiazol-3-one;
g) Glycol;
h) Xanthan gum;
i) Polyalkoxylated butyl ether.

[CLAIM 7]. The formulation comprising the synergistic composition as claimed in claim 4, wherein the Soluble Liquid (SL) formulation comprises:
a) Aromatic Hydrocarbon;
b) Polyalkoxylated butyl ether;
c) Polyethelene Glycol;
d) Trisiloxane Ethoxylate;
e) Silicon emulsion antifoam.

[CLAIM 8]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition is to be used to manage or control weeds control of Aeschynomene aspera, Aeschynomene indica, Ageratum conyzoides, Alternanthera sessilis, Alternanthera philoxeroides, Amaranthus spinosus, Amaranthus viridis, Ammania baccifera, Cynodon dactylon, Dactyloctenium aegyptium, Digitaria ciliaris, Digitaria setigera, Ischaemum rugosum, Echinochloa colona, Echinochloa crus-galli, Echinochloa glabrescens, Echinochloa crus-pavonis, Echinochloa esculenta, Echinochloa frumentacea, Echinochloa muricata, Echinochloa oryzoides, Echinochloa paludigena, Eleocharis kuruguwai, Laptochloa chinensis, Eleusine indica, Eclipta alba, Eclipta prostate, Imperata cylindrical, Leersia hexandra, Leptochloa chinensis, Oryza sativa, Panicum repens, Paspalum distichum, Paspalum scrobiculatum, Rottboellia cochinchinensis, Setaria glauca, Bolboschoenus maritimus, Bergia capensis, Commelina benghalensis, Commelina diffusa, Cyanotis axillaris, Eclipta alba, Eclipta prostrate, Eichhornia crassipes, Ipomoea aquatic, Ludwigia adscendens, Ludwigia hyssopifolia, Ludwigia octovalvis, Ludwigia parviflora, Marsilea minuta, Marsilea quadrifoliata, Mimosa diplotricha, Monochoria vaginalis, Pistia stratiotes, Polygonum hydropiper, Portulaca oleracea, Sagittaria milliacea, Sagittaria sagittifolia, Sphenoclea zeylanica, Trianthema portulacastrum, Typha spp., Isachne globosa, Paspalum distichum, Cyperus difformis, Cyperus haspen, Cyperus iria, Cyperus rotundus, Fimbristylis dichotoma, Fimbristylis miliacea, Scirpus juncoides, Scirpus nipponicus, Scirpus planiculmis, Scirpur royelei, Scirpus juncoides. The composition of present invention especially effective for control of Dactyloctenium aegyptium, Digitaria ciliaris, Ischaemum rugosum and Laptochloa chinensis, Oryza sativa (Red rice)

[CLAIM 9]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition control weeds in Paddy or Rice (Oryza sativa L.) including Indica, Japonica and Javanica race. GMO (Genetically Modified) Paddy, Sugarcane, Maize, Wheat