CN115915943A

CN115915943A - Herbicidal compositions, formulations and methods thereof

Info

Publication number: CN115915943A
Application number: CN202180044467.4A
Authority: CN
Inventors: 拉贾亚·斯里克里希南; 切穆图里·斯里德哈尔; 阿比吉特·博斯; 纳拉亚纳穆西·皮丘马尼
Original assignee: M/s Tacos Chemicals India Holding Co
Current assignee: M/s Tacos Chemicals India Holding Co
Priority date: 2020-04-22
Filing date: 2021-04-22
Publication date: 2023-04-04
Also published as: WO2021214792A1; CO2022015988A2

Abstract

The present disclosure provides a herbicidal composition comprising: 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1. The disclosure further provides formulations comprising the herbicidal compositions and methods of making the same. The present disclosure also provides methods for pre-emergence control of a broad spectrum of weeds in a field and weed control in a crop field.

Description

Herbicidal compositions, formulations and methods thereof

Technical Field

The present disclosure relates generally to crop improvement and management. More specifically, the present invention relates to a herbicidal composition for protecting crops from undesired vegetation and to the use of this composition. The disclosure further relates to a formulation comprising the herbicidal composition and a method of preparing the same.

Background

Controlling undesirable vegetation is a continuing effort to remove toxic/harmful weeds and thereby increase crop production. However, growing crops in the field presents several challenges to farmers because unwanted weeds have a negative impact on crop production and its yield. However, weeds are unwanted and undesirable plants that interfere with the use of land, water resources, and nutrients, and thus adversely affect human welfare by competing with beneficial and desirable vegetation of arable land, forests, aquatic systems, and the like, resulting in non-cultivated areas like industrial fields, road/rail lines, airports, landscape plantations, water tanks, waterways, and the like.

The study showed economic losses due to weeds in farm research trials conducted by the indian weed management coordination research program during 2003 to 2014 in major field crops in different areas of 18 nation in India ("Gharde, yogita, et al" Assessment of agricultural yield and economic losses due to weeds in India "[ Crop Protection ]107 (2018): 12-18). Studies have shown that the potential yield loss difference between different sites (bang) is large for direct seeded rice (15% -66%) and corn (18% -65%).

Controlling weeds may involve a wide range of techniques. One of the main techniques involves chemical treatment of weeds to control the germinating weed species by applying chemicals (herbicides) to the already germinating weeds or to the soil surface.

Herbicides are agents, usually chemicals, used to kill or inhibit the growth of unwanted plants, such as residential or agricultural weeds and invasive species. A great advantage of chemical herbicides compared to mechanical weed control is the ease of application, which generally saves labor costs. There are different types of herbicides known in the literature. For example, selective herbicides kill weed targets while leaving the desired crop relatively unharmed. On the other hand, some herbicides block certain plant hormone actions by interfering with the growth of weed plants. Herbicides can be applied by several methods and at different times during the growing period of the crop. Of these, four common herbicide application methods are pre-plant incorporation (PPI), pre-emergence, early post-emergence, and post-emergence. In pre-planting incorporation applications, the herbicide is sprayed and mixed in the topsoil before planting or sowing to achieve good weed control. Pre-emergence application corresponds to herbicide application immediately after sowing of the crop seeds or within 0-3 days of transplantation, before emergence of the weeds and crops from the soil surface. The early post-emergence herbicide is applied between 8 and 12 days after seeding the crop. Post-emergence application involves herbicide application after the crop and weeds emerge from the soil surface. Herbicides are classified and selected for application based on the type of crop, method of application, chemical characteristics of the herbicide, type of weed control (broadleaf, gramineous and sedge) and duration of weed control.

CA 2712696C discloses a herbicidal composition comprising the two active ingredients clodinafop-propargyl and metsulfuron-methyl in the form of granules with a hydrophobic inert coating material. WO 2012042316 A1 discloses a storage stable granular formulation comprising pyrazosulfuron ethyl, pretilachlor and sodium lignosulfonate.

Despite the many efforts made to develop herbicide compositions, there remains a need to address the stability of herbicides in relation to the combination of active ingredients. In addition, the prior art still suffers from deficiencies in providing enhanced compatibility between two or more active ingredients that show synergistic, more advantageous and desirable weed control benefits without affecting the plant health of the primary crop

Disclosure of Invention

In one aspect of the present disclosure, there is provided a herbicide composition comprising: (a) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (b) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In a second aspect of the disclosure, there is provided a formulation comprising: (a) a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1; and (b) an agronomically acceptable excipient, wherein the weight ratio of the herbicide composition to the agronomically acceptable excipient is in the range of 40.

In a third aspect of the disclosure, there is provided a formulation comprising: a) From 40% to 60% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) solvent, c) 2% to 10% (w/w) surfactant, d) 1% to 8% (w/w) anti-freeze agent, e) 0.1% to 0.5% (w/w) anti-foaming agent, f) 0.02% to 0.2% (w/w) biocide, g) 0.1% to 6% (w/w) polymer, and H) 7% to 25% (w/w) diluent, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range 1:1-1 10.

In a fourth aspect of the present disclosure, there is provided a formulation comprising: a) 40% to 60% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) water, c) 2% to 10% (w/w) surfactant, d) 1% to 8% (w/w) anti-freeze agent, e) 0.1% to 0.5% (w/w) anti-foaming agent, f) 0.02% to 0.2% (w/w) biocide, g) 0.1% to 6% (w/w) polymer, and H) 7% to 25% (w/w) diluent, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range 1:1-1 10.

In a fifth aspect of the present disclosure, there is provided a method of preparing a formulation comprising: (ii) (a) a herbicide composition and; (b) An agronomically acceptable excipient, the method comprising contacting the herbicide composition and the agronomically acceptable excipient to obtain the formulation, the herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1, wherein the weight ratio of the herbicidal composition to the agronomically acceptable excipients is in the range of 40 to 60.

In a sixth aspect of the present disclosure, there is provided a method for preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, a solvent and a diluent to form an emulsion; and mixing the suspension with the emulsion in the presence of a thickener and an acidic buffer to obtain the formulation.

In a seventh aspect of the present disclosure, there is provided a method for preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, water and a diluent to form an emulsion; and mixing the suspension with the emulsion in the presence of a thickening agent and an acidic buffer to obtain the formulation.

In an eighth aspect of the present disclosure, there is provided a method for pre-emergence control of a broad spectrum of weeds in a field, the method comprising applying a composition or formulation as disclosed herein.

In a ninth aspect of the disclosure, there is provided a method of weed control in a crop field comprising applying a composition or formulation as disclosed herein.

These and other features, aspects, and advantages of the present subject matter will become better understood with regard to the following description and appended claims. This summary is provided to introduce a selection of concepts in a simplified form. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

Detailed Description

Those skilled in the art will appreciate that variations and modifications of the present disclosure may be made in addition to those specifically described. It is to be understood that the present disclosure includes all such variations and modifications. The disclosure also includes all such steps, features, compositions and compounds, referred to or indicated in this specification, individually or collectively, and any and all combinations of any or more of such steps or features.

Definition of

For convenience, certain terms used in the specification and examples are described herein before the disclosure is further described. These definitions should be read in light of the remainder of this disclosure and as understood by those skilled in the art. Terms used herein have meanings that are recognized and known by those skilled in the art, however, for convenience and completeness, specific terms and their meanings are set forth below.

The articles "a" and "the" are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.

The terms "comprising" and "comprising" are used in an inclusive, open sense, and mean that additional elements may be included. It is not intended to be interpreted as "consisting only of … …".

Throughout this specification, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated element or step or group of elements or steps but not the exclusion of any other element or step or group of elements or steps.

The term "including" is used to mean "including but not limited to". "include" and "include but are not limited to" are used interchangeably.

The term "herbicide or herbicide" is a substance used to control unwanted vegetation. Selective herbicides control specific weed species while leaving the desired crop relatively unharmed, while non-selective herbicides can be used to clean wastelands, industrial and construction sites, and railroad embankments because they kill all plant material that comes into contact with them.

The term "fertilizing" as used herein refers to the addition of any natural or synthetic material to a plant or soil or plant to provide nutrients thereto to maintain its health.

The term "watering" as used herein refers to the addition of water to the soil of a plant.

The term "watering" as used herein means watering the plants to the following extent: water accumulates in the soil and rises to a certain height. This method of watering is commonly used in agriculture for growing rice crops.

The term "branches and leaves" as used herein refers to the leaves and stems of a plant.

The term "foliage spray" as used herein refers to a scheme of spraying onto the surface of a plant, covering the foliage and stems.

The term "broadcast" as used herein refers to a spray pattern that is mixed with sand or urea or any other carrier and spread evenly over the field or plants to ensure that the solution is spread in nearly equal amounts throughout the field or plants.

The term "antifreeze" as used herein refers to additives intended to lower the freezing point of a solution. They are added to the solution in order to make it suitable also for cold environments.

The term "antifoam" as used herein refers to an additive that reduces or retards the formation of foam in industrial process liquids.

The term "polymer" as used herein refers to a surfactant used to prepare a suspension of a material. For the purposes of this disclosure, the polymer used herein is a modified sodium lignosulfonate selected from the group consisting of Ufoxane 3A, ultrazine NA, vanisperse CB, or a combination thereof. The polymer was used to prepare a suspension of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide (sulfentrazone).

The term "thickener" as used herein refers to an additive used to increase the viscosity of a solution. The thickener may be one or a combination of more than one. In any individual case, suitable thickeners may be determined by one of ordinary skill in the art.

The term "biocide" as used herein refers to a chemical substance or microorganism that is intended to destroy, prevent, render harmless, or exert a controlling effect on: any harmful organisms like mycorrhiza (Mycorhizza), bacteria, fungi etc.

The term "acidic buffer" as used herein refers to a solution having a pH of less than 7 and containing a weak acid and one of its salts. When another acid or base is added to it, it resists any change in pH.

The term "diluent" as used herein refers to a liquid added to a material to reduce its viscosity and render the material free-flowing. In the present disclosure, the diluent is a continuous phase that facilitates ease of handling of the formulation when applied in the field. Diluents include, but are not limited to, water.

The term "carrier" as used herein refers to a substance that contains other substances to carry it to its desired location, such as the soil or the roots of a plant.

The term "safeners" are compounds used in combination with herbicides to make them safer, i.e. to reduce the effect of the herbicide on the crop plants and to increase the selectivity between the crop plants and the weed species the herbicide is directed against.

The term "syneresis" is a phenomenon in which any suspension formulation undergoes layer separation from the top down during its shelf life. A suspension formulation with minimal syneresis (i.e. minimal layer separation on top) means that it is physically stable throughout its shelf life.

The term "She Sunshang" as used herein refers to a defect in the leaves of a plant and may be due to chemical or herbicide spraying.

The term "wilting" as used herein means that the non-woody parts of the plant lose rigidity and also act to reduce water loss, as it exposes the leaves to less surface area.

The term "pulse-ming" as used herein refers to a condition that occurs as a result of the plant veins losing their normal green coloration, becoming unnaturally transparent or translucent, often later becoming yellow.

The term "necrosis" as used herein refers to a condition in which leaves, stems, or other parts are blackened and withered due to degeneration of cells or tissues.

The term "uploidy" as used herein refers to the inductive movement of plant parts in which downward bending of leaves or the like occurs due to different growth rates.

The term "downward bias" as used herein refers to an increase in growth of the lower part of the plant resulting in its upward curvature. Decentration is the upward bending of a leaf or other plant part due to increased growth of its lower surface.

The term "wet milling" as used herein refers to the process of grinding or pulverizing solid particles to disperse them in another liquid solution.

The term "cps" as used herein refers to SI units of viscosity, which is the abbreviation for centipoise, where one centipoise equals one millipascal second.

The term "precipitation" as used herein refers to the precipitation or deposition of a substance suspended, dispersed, or dissolved in another substance.

The term "EC" as used herein refers to an emulsifiable concentrate which is a liquid formulation containing one or more water-immiscible organic solvents and an emulsifier.

The term "emulsifier" as used herein refers to a surfactant that stabilizes an emulsion by increasing the degree of contact between two immiscible liquids in the emulsion.

The term "EW" as used herein refers to an oil-in-water emulsion in which a water insoluble oil phase is dispersed in water.

The term "effective amount" as used herein refers to the amount of the formulation that will kill the weeds. The "effective amount" will depend on, among other factors, the concentration of the formulation, the type of plant or plants being treated, the severity of the weed infestation, the desired result, and the life stage of the weed during treatment. Therefore, it is not always possible to specify an exact "effective amount". However, in any individual case, an appropriate "effective amount" can be determined by one of ordinary skill in the art.

The term "2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide" as used herein refers to sulfentrazone.

The term "2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide" as used herein refers to pretilachlor.

The unit "g a.i/ha" refers to the grams of active ingredient per hectare of field/area.

The term "crop field" refers to any field used for growing crops such as rice, direct seeded or germinated rice, transplanted rice, groundnut, potato, sugarcane, mint crops, or combinations thereof.

Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a weight range of 100-1500g a.i./ha should be understood to include not only the explicitly recited limit of 100g a.i./ha to 1500g a.i./ha, but also to include sub-ranges, such as 150-950g a.i./ha-, 200-800g a.i./ha, and the like, as well as individual amounts within the specified ranges, including fractional amounts, such as, for example, 150.2g a.i./ha and 900.2g a.i./ha.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. All publications mentioned herein are incorporated herein by reference.

Although 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide was used as the pre-emergence herbicide, it required moisture at the time of application or a slight irrigation after application to achieve its pre-emergence herbicidal activity. It is primarily the plant roots that absorb 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and susceptible plants die after emergence and exposure to light. 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is proposed to spray branches and leaves of the transplanted rice field 0 to 3 days after transplantation. Before application, the standing water is drained off and the herbicide is applied by means of a carpet-type foliage spray. The next day the water is again accumulated to achieve the desired result. This is a labor intensive application, putting much strain on farmers. 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, which has been used continuously for many years, does not provide effective and long-lasting control of a broad spectrum of weeds like broadleaf weeds, grasses and sedges. Even after application of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, farmers go through 2-3 rounds of manual weeding, which is expensive practice. Furthermore, manual weeding is a significant challenge as no labor is available.

In transplanting rice, the main weeds are grasses and sedges, followed by broadleaf weeds. However, the weed field varies depending on the specific area, soil type, water availability and mode of use of the herbicide in the last few years. The main weeds of the gramineous species in rice are paspalum, moleplant seed. The main weeds of the broad-leaved species are monochoria vaginalis, ludwigia tenuifolia, dayflower, eclipta prostrata and jiejia cambogia. The main weeds of the cyperus rotundus varieties are cyperus rotundus, cyperus heterophyllus, scirpus yagara and waterweed.

Over the years, other pre-emergence herbicides and combinations thereof introduced by companies were not as effective as 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, but were only effective against specific species of weeds, and continued use of these herbicides resulted in weed resistance to these herbicides. In this context, there is an urgent need to identify a suitable herbicide with different modes of action applicable on a wide variety of weed plants, and a combination partner to provide more advantageous control of spectral weeds, including longer duration control and increased resistance factors for herbicides. However, 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide from the aniline family and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide from the chloroacetanilide family, delivered with all water as a continuous medium, have their own challenges, particularly due to the chemical instability of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide. 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is commercially available as an EC, EW formulation in which the diluent is an aromatic petroleum hydrocarbon. However, water-based formulations of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide and in combination with another herbicide component are not available due to the inherent challenges of formulation. 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, one of the components of the formulation, has a strong tendency to decompose over a period of time, resulting in an unstable formulation. Thus, when combined with 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide, it is a significant challenge to maintain 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide activity stable throughout the shelf life of the pre-mixed formulation product. It has been surprisingly found that by dispersing emulsified droplets dispersed in a suspension containing very fine particles of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide, a suspoemulsion is ultimately produced. In addition, the formulations provided in the present disclosure are stable in water as a solvent, which makes the formulations more advantageous, cost effective, and easy to use. The disclosed formulations are user and environmentally friendly. In addition, the present disclosure also emphasizes the stability of the formulation in water as a weight percentage of its components.

Thus, in view of the above-mentioned disadvantages inherent in the currently known products and applications as mentioned above, the present disclosure overcomes the disadvantages of the prior art disclosures and provides a composition comprising two active ingredients, namely 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, and a formulation comprising the above-mentioned composition with an agronomically acceptable excipient. The compositions and formulations of the present disclosure are stable suspoemulsion herbicide compositions. The compositions of the present disclosure are formulated to contain excipients, such as solvents, anti-caking agents, stabilizers, anti-foaming agents, slip agents, humectants, dispersing agents, wetting agents, thickening agents, emulsifiers, and preservatives, that increase the long-lasting activity of the active. Other components that enhance the biological activity of these ingredients may optionally be included.

The scope of the present disclosure is not to be limited by the specific embodiments described herein, which are intended as illustrations only. Functionally equivalent products, compositions, and methods are clearly within the scope of the present disclosure, as described herein.

The present disclosure discloses a herbicide composition/formulation comprising 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide as active ingredients in certain specific ratios. The present disclosure refers to sulfentrazone as 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and pretilachlor as 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide. In addition, a formulation comprising a composition of the present disclosure and an agronomically acceptable excipient is also disclosed. The agronomically acceptable excipient is selected from the group consisting of (a) a solvent, (b) a surfactant, (c) a cryoprotectant, (d) an antifoam, (e) a thickener, (f) a biocide, (g) a polymer, (h) an acidic buffer, or combinations thereof. The disclosure further discloses a method of applying the formulation as a pre-emergence application in the form of a suspoemulsion to control a broad spectrum of weeds in a field with different types of soil, clay loam or sandy loam planted with a rice crop.

In an embodiment of the present disclosure, there is provided a herbicide composition comprising: (a) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (b) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the present disclosure, there is provided a herbicide composition comprising: (a) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (b) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1. In another embodiment of the disclosure, the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1. In another embodiment of the disclosure, the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1:5. In another embodiment of the disclosure, the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1:2.

In an embodiment of the disclosure, there is provided a formulation comprising: (a) a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1; and (b) an agronomically acceptable excipient, wherein the weight ratio of the herbicide composition to the agronomically acceptable excipient is in the range of 40.

In an embodiment of the disclosure, there is provided a formulation comprising: (a) a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1; and (b) an agronomically acceptable excipient, wherein the weight ratio of the herbicide composition to the agronomically acceptable excipient is in the range of 42. In another embodiment of the disclosure, there is provided a formulation as disclosed herein, wherein the weight ratio of the herbicide composition to the agronomically acceptable excipient is in the range of 44. In yet another embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the weight ratio of the herbicide composition to the agronomically acceptable excipient is in the range of 45. In another embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the weight ratio of the herbicide composition to the agronomically acceptable excipient is 46. In another embodiment of the disclosure, there is provided a formulation as disclosed herein, wherein the weight ratio of the herbicide composition to the agronomically acceptable excipient is 47.

In an embodiment of the disclosure, there is provided a formulation comprising: (a) a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1; and (b) an agronomically acceptable excipient selected from a solvent, surfactant, cryoprotectant, antifoam, thickener, biocide, polymer, acidic buffer, diluent, or a combination thereof.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) From 40% to 60% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) of a solvent; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an antifreeze; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; and H) 7% to 25% (w/w) of a diluent wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) 42% to 58% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 5% to 25% (w/w) of a solvent; c) 4% to 9% (w/w) of a surfactant; d) 2% to 6% (w/w) of an anti-freeze agent; e) 0.1% to 0.4% (w/w) of an antifoaming agent; f) 0.05% to 0.2% (w/w) of a biocide; g) 0.1% to 5% (w/w) of a polymer; and H) 10% to 20% (w/w) of a diluent, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) 45% to 55% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 10% to 20% (w/w) of a solvent; c) 5% to 9% (w/w) of a surfactant; d) 3% to 6% (w/w) of an anti-freeze agent; e) 0.2% to 0.4% (w/w) of an antifoaming agent; f) 0.1% to 0.2% (w/w) of a biocide; g) 0.1% to 4% (w/w) of a polymer; and H) 15% to 20% (w/w) of a diluent wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1:5.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) From 40% to 60% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) water; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an antifreeze; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; and H) 7% to 25% (w/w) of a diluent wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) 42% to 58% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 5% to 25% (w/w) water; c) 4% to 9% (w/w) of a surfactant; d) 2% to 6% (w/w) of an anti-freeze agent; e) 0.1% to 0.4% (w/w) of an antifoaming agent; f) 0.05% to 0.2% (w/w) of a biocide; g) 0.1% to 5% (w/w) of a polymer; and H) 10% to 20% (w/w) of a diluent, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) 45% to 55% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 10% to 20% (w/w) water; c) 5% to 9% (w/w) of a surfactant; d) 3% to 6% (w/w) of an anti-freeze agent; e) 0.2% to 0.4% (w/w) of an antifoaming agent; f) 0.1% to 0.2% (w/w) of a biocide; g) 0.1% to 4% (w/w) of a polymer; and H) 15% to 20% (w/w) of a diluent wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1:5.

In an embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the formulation further comprises 0.05% to 2% (w/w) of a thickening agent; 6% to 12% (w/w) of a safener; and 0.1% to 2% (w/w) of an acidic buffer. In another embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the formulation further comprises 0.1% to 1% (w/w) of a thickening agent; 7% to 11% (w/w) of a safener; and 0.1% to 2% (w/w) of an acidic buffer.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) 40% to 60% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) of a solvent; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an anti-freeze agent; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; h) 7% to 25% (w/w) of a diluent, i) 0.05% to 1% (w/w) of a thickener; and j) 7% to 11% (w/w) of a safener, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) From 40% to 60% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) of a solvent; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an anti-freeze agent; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; h) 7% to 25% (w/w) of a diluent, i) 0.05% to 1% (w/w) of a thickener; j) 7% to 11% (w/w) of a safener; and k) 0.1% to 2% (w/w) of an acidic buffer, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) From 40% to 60% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) water; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an anti-freeze agent; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; h) 7% to 25% (w/w) of a diluent, i) 0.05% to 1% (w/w) of a thickener; and j) 7% to 11% (w/w) of a safener, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a formulation, wherein the formulation comprises: a) From 40% to 60% (w/w) of a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) water; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an anti-freeze agent; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; h) 7% to 25% (w/w) of a diluent, i) 0.05% to 1% (w/w) of a thickener; j) 7% to 11% (w/w) of a safener; and k) 0.1% to 2% (w/w) of an acidic buffer, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a formulation as disclosed herein, wherein the solvent is selected from a C8-C10 dimethylamide fatty acid, a C9-C12 aromatic petroleum hydrocarbon, water, or a combination thereof. In another embodiment of the disclosure, the C8-C10 dimethylamide fatty acid is selected from Agnique AMD12, agnique AMD 810, hallcommid 1225, rhodiasolve ADMA810 (solvent 810), rhodiasolve ADMA10 (solvent ADMA 10), gene 4166 (solvent 4166), gene 4296 (solvent 4296), or a combination thereof. In another embodiment of the present disclosure, the C9-C12 aromatic petroleum hydrocarbon is selected from the group consisting of solvents C-IX, solvesso 100, solvesso 150, solvesso 200, solvesso 150ND, solvesso 200ND, or combinations thereof.

In an embodiment of the disclosure, there is provided a formulation as disclosed herein, wherein the solvent is selected from the group consisting of Genagen 4266, solvent C-IX, solvesso 100, solvent 4166, solvent 810, solvent C-IX, water, or a combination thereof. In another embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the solvent is selected from Genagen 4266, solvent C-IX, solvesso 100, solvent 4166, solvent 810, solvent C-IX, or a combination thereof. In yet another embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the solvent is water.

In an embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the surfactant is selected from butyl block copolymers, alkyl benzene sulfonates, castor oil ethoxylates, tristyrylphenol ethoxylates, sodium alkyl naphthalene sulfonate-formaldehyde condensates, acrylic acid copolymer solutions, or combinations thereof. In another embodiment of the present disclosure, the butyl block copolymer is selected from Emulsogen 3510, agnique CSO, toximul 8321, step flow 26, soprophor 796P, soprophor TSP/461, atlas G5000, pluronic PE10300, or combinations thereof. In another embodiment of the disclosure, the alkylbenzene sulfonate is selected from Rhodacal 70C, rhodacal BC, calsogen AR100ND, calsogen ARL100ND, phonyl Sulphonate CA, phonyl Sulphonate CAL, unitop Unicaps 7060, unicaps 7030, rhodacal 60/BE, rhodacal65/BR, or combinations thereof. In another embodiment of the present disclosure, the castor oil ethoxylate is selected from Emulsogen EL360, alkamuls OR36, agnique CSO 35, OR a combination thereof. In another embodiment of the present disclosure, the tristyrylphenol ethoxylate is selected from the group consisting of unicop W20, noigen AB90, soprophor BSU CR, or a combination thereof. In another embodiment of the present disclosure, the sodium alkylnaphthalene sulfonate-formaldehyde condensate is selected from Supragil MNS90, tersperse 2020, morwet D425, igsurf 2080DW, unicop dispersox LS, or combinations thereof. In another embodiment of the present disclosure, the acrylic copolymer solution is selected from Atlox 4913, atlox 4914, tersperse 2500, or combinations thereof. In yet another embodiment of the disclosure, the surfactant is selected from atlas g5000, rhodacal 70C, calsogen AR100, emulsogen 3510, atlox 4913, morwet D425, igsurf 2080DW, unitop Dispertox LS, atlox 4914, or a combination thereof. In yet another embodiment of the present disclosure, the surface activity is selected from atlas g5000, atlox 4914, or a combination thereof.

In an embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the cryoprotectant is selected from the group consisting of glycerol, propylene glycol, or a combination thereof. In another embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the cryoprotectant is propylene glycol.

In an embodiment of the disclosure, there is provided a formulation as disclosed herein, wherein the antifoam is a silicone emulsion and wherein the silicone emulsion is selected from Rhodorsil Silcolapse 5020, sag 1572, sag 10, sag 30, rhodorsil 432, or a combination thereof. In another embodiment of the disclosure, a formulation is provided wherein the anti-foaming agent is Sag 1572.

In an embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the thickening agent is selected from xanthan gum, polysaccharides, cellulosic materials, hydrophilic fumed silica, hydrated magnesium silica, sodium aluminosilicate, or combinations thereof. In another embodiment of the present disclosure, the thickening agent is xanthan gum. In another embodiment of the disclosure, the polysaccharide is Rhodopol. In another embodiment of the present disclosure, the cellulosic material is carboxymethyl cellulose. In another embodiment of the present disclosure, the hydrophilic fumed silica is selected from the group consisting of Cab-O-sil H-5, cab-O-sil EH-5, cab-O-sil M-5, and combinations thereof. In another embodiment of the present disclosure, the hydrated magnesium silicate is Veegum. In another embodiment of the present disclosure, the sodium aluminosilicate is Tixolex 28.

In an embodiment of the disclosure, there is provided a formulation as disclosed herein, wherein the biocide is selected from Nipacide CI 15, proxel GXL, or a combination thereof. In another embodiment of the disclosure, there is provided a formulation as disclosed herein, wherein the biocide is Proxel GXL.

In an embodiment of the disclosure, there is provided a formulation as disclosed herein, wherein the polymer is a modified sodium lignosulfonate and wherein the modified sodium lignosulfonate is selected from Ufoxane 3A, ultrazine NA, vanisperse CB, or a combination thereof. In another embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the polymer is modified sodium lignosulfonate and the modified sodium lignosulfonate is Ultrazine NA.

In an embodiment of the disclosure, there is provided a formulation as disclosed herein, wherein the acidic buffer is selected from citric acid, acetic acid, sodium acetate, sodium citrate, boric acid, or a combination thereof. In another embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the acidic buffer is citric acid.

In an embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the formulation further comprises a safener selected from the group consisting of fenclorim, pyrazolysetinic acid, isoxadifen, clethodim, cloquintocet mexyl, or a combination thereof. In another embodiment of the present disclosure, there is provided a formulation as disclosed herein, wherein the safener is fenclorim.

In an embodiment of the present disclosure, there is provided a suspoemulsion formulation as disclosed herein, wherein the formulation further comprises a carrier. In another embodiment of the present disclosure, the carrier is selected from urea, sand, or a combination thereof.

In an embodiment of the disclosure, there is provided a method of preparing a formulation comprising: (a) a herbicidal composition and; (b) An agronomically acceptable excipient, the method comprising contacting the herbicide composition and the agronomically acceptable excipient to obtain the formulation, the herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1; wherein the weight ratio of the herbicide composition to the agronomically acceptable excipient is in the range of 40.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, a solvent and a diluent to form an emulsion; and c) mixing the suspension with the emulsion to obtain the formulation.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, a solvent and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickening agent to obtain the formulation.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, a solvent and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickening agent and an acidic buffer to obtain the formulation.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, a solvent and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickening agent, an acidic buffer and a safener to obtain the formulation.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, a solvent and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickener and an acidic buffer to obtain the formulation and wherein mixing the suspension with the emulsion is performed at a stirring speed in the range of 200 to 400rpm for a time period in the range of 20 to 120 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, a solvent and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickener and an acidic buffer to obtain the formulation and wherein mixing the suspension with the emulsion is performed at a stirring speed in the range of 250 to 350rpm for a time period in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 10% to 40% (w/w) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with 2% to 10% (w/w) surfactant, 1% to 8% (w/w) antifreeze agent, 0.1% to 0.5% (w/w) antifoam agent, 0.1% to 6% (w/w) polymer, 0.02% to 0.2% (w/w) biocide, and 7% to 25% (w/w) diluent to form a suspension; b) Contacting 10% to 50% (w/w) of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with 2% to 10% (w/w) of a surfactant, 2% to 30% (w/w) of a solvent, and 7% to 25% (w/w) of a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of 0.05% to 2% (w/w) of a thickening agent to obtain the formulation and wherein mixing the suspension with the emulsion is carried out at a stirring speed in the range of 250 to 350rpm for a time period in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 10% to 40% (w/w) of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with 2% to 10% (w/w) of a surfactant, 1% to 8% (w/w) of an antifreeze agent, 0.1% to 0.5% (w/w) of an antifoam agent, 0.1% to 6% (w/w) of a polymer, 0.02% to 0.2% (w/w) of a biocide, and 7% to 25% (w/w) of a diluent to form a suspension; b) Contacting 10% to 50% (w/w) of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with 2% to 10% (w/w) of a surfactant, 2% to 30% (w/w) of a solvent and 7% to 25% (w/w) of a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of 0.05% to 2% (w/w) of a thickening agent and 0.1% to 2% (w/w) of an acidic buffer to obtain the formulation and wherein mixing the suspension with the emulsion is carried out at a stirring speed in the range of 250 to 350rpm for a period of time in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 10% to 35% (w/w) of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with 2% to 10% (w/w) of a surfactant, 1% to 8% (w/w) of an antifreeze agent, 0.1% to 0.5% (w/w) of an antifoam agent, 0.1% to 6% (w/w) of a polymer, 0.02% to 0.2% (w/w) of a biocide, and 7% to 25% (w/w) of a diluent to form a suspension; b) Contacting 10% to 30% (w/w) of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with 2% to 10% (w/w) of a surfactant, 2% to 30% (w/w) of a solvent and 7% to 25% (w/w) of a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of 0.05% to 2% (w/w) of a thickening agent, 0.1% to 2% (w/w) of an acidic buffer and 6% to 12% (w/w) of a safener to obtain the formulation and wherein mixing the suspension with the emulsion is carried out at a stirring speed in the range of 250 to 350rpm for a period of time in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 15% to 20% (w/w) of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with 2% to 10% (w/w) of a surfactant, 1% to 8% (w/w) of an antifreeze agent, 0.1% to 0.5% (w/w) of an antifoam agent, 0.1% to 6% (w/w) of a polymer, 0.02% to 0.2% (w/w) of a biocide, and 7% to 25% (w/w) of a diluent to form a suspension; b) Contacting 20% to 35% (w/w) of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with 2% to 10% (w/w) of a surfactant, 2% to 30% (w/w) of a solvent, and 7% to 25% (w/w) of a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of 0.05% to 2% (w/w) of a thickening agent, 0.1% to 2% (w/w) of an acidic buffer and 6% to 12% (w/w) of a safener to obtain the formulation and wherein mixing the suspension with the emulsion is carried out at a stirring speed in the range of 250 to 350rpm for a period of time in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, water and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickening agent to obtain the formulation.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, water and a diluent to form an emulsion; and c) mixing the suspension with the emulsion to obtain the formulation.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, water and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickening agent to obtain the formulation.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, water and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickening agent and an acidic buffer to obtain the formulation.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, water and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickening agent, an acidic buffer and a safener to obtain the formulation.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, water and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickener to obtain the formulation and wherein mixing the suspension with the emulsion is carried out at a stirring speed in the range of 200 to 400rpm for a time period in the range of 20 to 120 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension; b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, water and a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of a thickener and an acidic buffer to obtain the formulation and wherein mixing the suspension with the emulsion is performed at a stirring speed in the range of 250 to 350rpm for a time period in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 10% to 40% (w/w) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with 2% to 10% (w/w) surfactant, 1% to 8% (w/w) antifreeze agent, 0.1% to 0.5% (w/w) antifoam agent, 0.1% to 6% (w/w) polymer, 0.02% to 0.2% (w/w) biocide, and 7% to 25% (w/w) diluent to form a suspension; b) Contacting 20% to 50% (w/w) of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with 2% to 10% (w/w) of a surfactant, 2% to 30% (w/w) of water and 7% to 25% (w/w) of a diluent to form an emulsion; and c) mixing the suspension with the emulsion to obtain the formulation and wherein mixing the suspension with the emulsion is performed at a stirring speed in the range of 250 to 350rpm for a time period in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 15% to 20% (w/w) of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with 2% to 10% (w/w) of a surfactant, 1% to 8% (w/w) of an antifreeze agent, 0.1% to 0.5% (w/w) of an antifoam agent, 0.1% to 6% (w/w) of a polymer, 0.02% to 0.2% (w/w) of a biocide, and 7% to 25% (w/w) of a diluent to form a suspension; b) Contacting 20% to 35% (w/w) of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with 2% to 10% (w/w) of a surfactant, 2% to 30% (w/w) of water and 7% to 25% (w/w) of a diluent to form an emulsion; and c) mixing the suspension with the emulsion to obtain the formulation and wherein mixing the suspension with the emulsion is performed at a stirring speed in the range of 250 to 350rpm for a time period in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 10% to 40% (w/w) of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with 2% to 10% (w/w) of a surfactant, 1% to 8% (w/w) of an antifreeze agent, 0.1% to 0.5% (w/w) of an antifoam agent, 0.1% to 6% (w/w) of a polymer, 0.02% to 0.2% (w/w) of a biocide, and 7% to 25% (w/w) of a diluent to form a suspension; b) Contacting 20% to 50% (w/w) of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with 2% to 10% (w/w) of a surfactant, 2% to 30% (w/w) of water and 7% to 25% (w/w) of a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of 0.05% to 2% (w/w) of a thickener to obtain the formulation and wherein mixing the suspension with the emulsion is performed at a stirring speed in the range of 250 to 350rpm for a time period in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 10% to 40% (w/w) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with 2% to 10% (w/w) surfactant, 1% to 8% (w/w) antifreeze agent, 0.1% to 0.5% (w/w) antifoam agent, 0.1% to 6% (w/w) polymer, 0.02% to 0.2% (w/w) biocide, and 7% to 25% (w/w) diluent to form a suspension; b) Contacting 20% to 50% (w/w) of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with 2% to 10% (w/w) of a surfactant, 2% to 30% (w/w) of water and 7% to 25% (w/w) of a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of 0.05% to 2% (w/w) of a thickening agent and 0.1% to 2% (w/w) of an acidic buffer to obtain the formulation and wherein mixing the suspension with the emulsion is carried out at a stirring speed in the range of 250 to 350rpm for a period of time in the range of 20 to 100 minutes.

In an embodiment of the disclosure, there is provided a method of preparing a formulation, the method comprising: a) Contacting 10% to 40% (w/w) of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with 2% to 10% (w/w) of a surfactant, 1% to 8% (w/w) of an antifreeze agent, 0.1% to 0.5% (w/w) of an antifoam agent, 0.1% to 6% (w/w) of a polymer, 0.02% to 0.2% (w/w) of a biocide, and 7% to 25% (w/w) of a diluent to form a suspension; b) Contacting 20% to 50% (w/w) of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with 2% to 10% (w/w) of a surfactant, 2% to 30% (w/w) of water and 7% to 25% (w/w) of a diluent to form an emulsion; and c) mixing the suspension with the emulsion in the presence of 0.05% to 2% (w/w) of a thickening agent, 0.1% to 2% (w/w) of an acidic buffer and 6% to 12% (w/w) of a safener to obtain the formulation and wherein mixing the suspension with the emulsion is carried out at a stirring speed in the range of 250 to 350rpm for a period of time in the range of 20 to 100 minutes.

In an embodiment of the present disclosure, there is provided a method for preemergence control of a broad spectrum of weeds in a field comprising applying a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a method for preemergence control of a broad spectrum of weeds in a field, the method comprising applying a formulation comprising: (a) a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide and; (b) an agronomically acceptable excipient. In another embodiment of the present disclosure, the site includes a site having clay loam, sand loam, and combinations thereof. In another embodiment of the present disclosure, the site includes a site having different types of soil.

In an embodiment of the disclosure, there is provided a method for preemergence control of a broad spectrum of weeds in a field comprising applying a formulation comprising: (a) From 40% to 60% (w/w) of a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) of a solvent; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an anti-freeze agent; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; and h) 7% to 25% (w/w) of a diluent.

In an embodiment of the disclosure, there is provided a method for preemergence control of a broad spectrum of weeds in a field, the method comprising applying a formulation comprising: (a) From 40% to 60% (w/w) of a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) of a solvent; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an antifreeze; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; h) 7% to 25% (w/w) of a diluent; i) 0.1% to 2% (w/w) of an acidic buffer; j) 0.05% to 2% (w/w) of a thickener; and k) 6% to 12% (w/w) of a safener.

In an embodiment of the disclosure, there is provided a method for preemergence control of a broad spectrum of weeds in a field, the method comprising applying a formulation comprising: (a) From 40% to 60% (w/w) of a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) water; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an anti-freeze agent; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; and h) 7% to 25% (w/w) of a diluent.

In an embodiment of the disclosure, there is provided a method for preemergence control of a broad spectrum of weeds in a field, the method comprising applying a formulation comprising: (a) From 40% to 60% (w/w) of a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; b) 2% to 30% (w/w) water; c) 2% to 10% (w/w) of a surfactant; d) 1% to 8% (w/w) of an anti-freeze agent; e) 0.1% to 0.5% (w/w) of an antifoaming agent; f) 0.02% to 0.2% (w/w) of a biocide; g) 1% to 6% (w/w) of a polymer; h) 7% to 25% (w/w) of a diluent; i) 0.1% to 2% (w/w) of an acidic buffer; j) 0.05% to 2% (w/w) of a thickener; and k) 6% to 12% (w/w) of a safener.

In an embodiment of the disclosure, there is provided a method for pre-emergence control of a broad spectrum of weeds in clay loam, the method comprising applying a formulation comprising: (a) a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide and; (b) an agronomically acceptable excipient.

In an embodiment of the present disclosure, there is provided a method for preemergence control of a broad spectrum of weeds in clay loam, the method comprising applying a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, there is provided a method for preemergence control of a broad spectrum of weeds in sandy loam comprising applying a formulation comprising: (a) a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide and; (b) an agronomically acceptable excipient.

In an embodiment of the present disclosure, there is provided a method for preemergence control of a broad spectrum of weeds in sandy loam comprising applying a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In embodiments of the disclosure, there is provided a method of weed control in crop fields, the method comprising applying to the crop fields a formulation comprising: (a) a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide and; (b) an agronomically acceptable excipient.

In embodiments of the present disclosure, there is provided a method of weed control in paddy fields, the method comprising applying between the paddy fields a formulation comprising: (a) a herbicidal composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide and; (b) an agronomically acceptable excipient.

In embodiments of the present disclosure, there is provided a method of weed control in crop fields, the method comprising applying to the crop fields a herbicide composition comprising: (i) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and (ii) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide and; (b) An agronomically acceptable excipient wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

In an embodiment of the disclosure, a method for preemergence control of a broad spectrum of weeds in a field is provided, comprising applying the formulation at a use rate of 0.2-4.0kg/ha in the fields.

In an embodiment of the disclosure, a method for preemergence control of a broad spectrum of weeds in a field is provided, the method comprising applying the formulation in the fields to provide a total weight of the herbicide composition in the range of 100-1500g a.i./ha. In another embodiment of the present disclosure, a method for preemergence control of a broad spectrum of weeds in a field is provided, the method comprising applying the formulation in the field fields to provide a total weight of herbicide composition in the range of 100-1300g a.i./ha. In yet another embodiment of the present disclosure, a method for preemergence control of a broad spectrum of weeds in a field is provided, the method comprising applying the formulation in the field fields to provide a total weight of herbicide composition in the range of 100-1000g a.i./ha.

In an embodiment of the present disclosure, a method for preemergence control of a broad spectrum of weeds in a field is provided, the method comprising applying the formulation in the field fields to provide a total weight of herbicide composition in the range of 100-1500g a.i./ha, wherein the total weight of herbicide composition comprises 100-300g a.i./ha of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 150-450g a.i./ha of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide.

In embodiments of the present disclosure, a method of weed control in crop fields is provided, the method comprising applying the formulation in the field fields to provide a total weight of herbicide composition in the range of 100-1500g a.i./ha.

In embodiments of the disclosure, a method of weed control in a crop field is provided that includes applying the formulation in various types of soil at the time of application of direct-seeded or transplanted rice in the fields.

In an embodiment of the disclosure, a method of weed control in a crop field is provided, the method comprising applying the formulation in a field of a directly sown or germinated rice, transplanted rice, groundnut, potato, sugarcane, mint crop, or a combination thereof. In another embodiment of the disclosure, a method of weed control in a crop field is provided comprising applying the formulation in a field where a rice, transplanted rice, groundnut, potato, sugarcane, or mint crop is directly sown or germinated.

In embodiments of the present disclosure, the compositions of the present disclosure may be formulated in various ways, depending on which biological and/or chemical-physical parameters are predetermined. Possible formulation options are, for example, wettable Powders (WP), emulsifiable Concentrates (EC), aqueous Solutions (SL), emulsions (EW) such as oil-in-water sprayable solutions or emulsions, oil-based or water-based dispersions, suspoemulsions (SE), water dispersible granules (WG), mixed formulations of Capsule Suspensions (CS) and Emulsions (EW), i.e. ZW formulations, ULV formulations, microcapsules or waxes.

In embodiments of the disclosure, the compositions of the disclosure may be formulated as a water dispersible granule (WG) formulation comprising: (1) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; (2) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; and (3) an agronomically acceptable excipient selected from the group consisting of: at least one dispersant, (b) at least one wetting agent, (c) at least one absorbent, (d) at least one antifoaming agent, (e) at least one buffering agent, (f) at least one filler, and combinations thereof.

In embodiments of the present disclosure, compositions of the present disclosure may be formulated as Emulsifiable Concentrate (EC) formulations comprising: (1) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; (2) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; and (3) an agronomically acceptable excipient selected from the group consisting of: at least one solvent, (b) at least one co-solvent, (c) at least one surfactant, (d) at least one co-surfactant, (e) at least one stabilizer, and combinations thereof.

In embodiments of the present disclosure, compositions of the present disclosure may be formulated as Wettable Powder (WP) formulations comprising: (1) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; (2) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; and (3) an agronomically acceptable excipient selected from the group consisting of: at least one dispersant, (b) at least one wetting agent, (c) at least one absorbent, (d) at least one antifoaming agent, (e) at least one buffering agent, (f) at least one filler, (g) at least one stabilizer, and combinations thereof.

In embodiments of the present disclosure, compositions of the present disclosure may be formulated as Emulsions (EW), such as oil-in-water formulations, comprising: (1) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; (2) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; and (3) an agronomically acceptable excipient selected from the group consisting of: at least one surfactant, (c) at least one co-surfactant, (d) at least one anti-freeze agent, (e) at least one anti-foam agent, (f) at least one stabilizer, (g) at least one diluent, (h) at least one thickener, (i) at least one biocide, and combinations thereof.

In embodiments of the present disclosure, the compositions of the present disclosure may be formulated as a mixed formulation of Capsule Suspension (CS) and aqueous Emulsion (EW), i.e., a ZW formulation, comprising: (1) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; (2) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide; and (3) an agronomically acceptable excipient selected from the group consisting of: at least one co-solvent, (b) at least one co-solvent, (c) at least one surfactant, (d) at least one co-surfactant, (e) at least one anti-freeze agent, (f) at least one anti-foam agent, (g) at least one phase stabilizer, (h) at least one diluent, (i) at least one thickener, (j) at least one biocide, (k) at least one oil-soluble monomer, (l) at least one water-soluble monomer, (m) at least one dispersant, (n) at least one protective colloid, (o) at least one acidic buffer, and combinations thereof.

In embodiments of the present disclosure, compositions/formulations as described herein may be included with other pesticide actives such as fungicides, pesticides, herbicides or insecticides, safeners, fertilizers, growth regulators, and combinations thereof. In another embodiment of the present disclosure, the composition/formulation may be used in the form of a pre-made formulation or as a tank mix.

In embodiments of the present disclosure, the compositions/formulations as described herein may be applied to plants, plant parts, soil, plant seeds, and combinations thereof.

In embodiments of the present disclosure, the compositions/formulations as described herein may be administered by a method selected from: seeding with a carrier, seeding with sand, seeding with urea, foliage spraying, basal peeling, boom sprayer, aerial spraying, sprayer, carpet wiper, wick applicator, weed extractor, backpack sprayer, spot spraying, peeling, manual thinning, wick wiping, or combinations thereof.

Although the subject matter has been described in considerable detail with reference to certain examples and implementations thereof, other implementations are possible.

Examples of the invention

The disclosure will now be illustrated with working examples, which are intended to illustrate the disclosed work and are not intended to be taken to imply any limitation as to the scope of the disclosure in a limiting sense. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice of the disclosed methods and compositions, the exemplary methods, devices, and materials are described herein. It is to be understood that this disclosure is not limited to the particular methods and experimental conditions described, as such methods and conditions may apply.

Working and non-working examples as described in the next section highlight the criticality of the working percentages of the different components in achieving the herbicide compositions/formulations of the present disclosure. It is further indicated that the presence of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide are critical to the implementation of the herbicide compositions/formulations of the present invention. The absence of any of the above-identified components or the replacement of these components with any other component greatly affects the efficacy of the compositions/formulations in terms of phytotoxicity, weed control and yield attribute parameters of the crop.

Materials and methods

Field trials were conducted at three sites, namely, eangstrom Lu Luhe Nerolor at Androgram, india and Gooderol at Tamil Nadelpon to evaluate the efficacy of the formulations of the present invention for weed suppression and to find the appropriate dosage of the herbicide composition/formulation and its effect on transplanted rice. Different varieties of rice are transplanted in each field. The pre-field crop is also maintained as rice. Rice crops are grown using the normal set of practices in the respective areas under field conditions, such as fertilization, pest control, watering and maintenance, to ensure good growth of the crops and weeds. The test was performed with 10 treatments. Four of the replicates were used to record phytotoxicity observations, while three were used for other biometric parameters to account for reproducibility of results. These treatments were applied only once, the next day after transplantation. Treatments comprising 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide were mixed in the desired amount of sand or urea and spread on crop/paddy fields with water accumulation. Treatments of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide, penoxsulam (penoxsulam), and combinations thereof are applied in a carpet-leaf pre-emergence application. For each treatment, an appropriate amount of area of the treated plot was made to achieve the desired application rate based on the unit area (hectare) of the calculated and measured application. The sand or urea required to treat the desired area is collected. The required amount of chemical is mixed well with the sand or urea. And (3) spreading the chemically treated sand or urea in the accumulated water in the field. This chemical dissolves in the water and forms a layer on the soil surface. By this method, the contact of chemicals with the branches and leaves is minimized. Treatments were rated and compared to manual herbicidal treatment (no weeds), weed check (water spray) and standard herbicide treatment (commercially popular and recommended).

2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide 39.6% SC, 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide 50% EC, penoxsulam 21.7% SC, and penoxsulam 1.97% + butachlor 38.8% SE are standard benchmark formulations, purchased from local markets and commercially recommended. The desired amount of chemical is removed and mixed in the desired amount of water and sprayed.

In general, the combination of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide within the disclosed weight ranges is critical to achieving the desired performance of the herbicide composition/formulation. Even the use of another component in place of a single component does not provide the desired effect. In addition, deviations from the disclosed weight ranges do not show the desired results.

The following example illustrates how the present disclosure provides a herbicide composition/formulation comprising 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide (sulfentrazone) and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide (pretilachlor) as active ingredients. Also described is a formulation comprising the herbicide composition/formulation, an agronomically acceptable excipient and a carrier. Studies are provided to support the stability of the formulation. Examples also include methods of obtaining and making the compositions and formulations. Further included is a method of applying the formulation in a field having clay loam and sandy loam in which a rice crop is transplanted. Studies have been conducted in different agricultural climates to understand their efficacy and dose optimization in different types of soil.

Example 1

Preparation of formulations (suspoemulsions) of the disclosure

A herbicidal composition/formulation comprising 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide 200 and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide 300g/L SE was prepared and this composition/formulation was then used in the preparation of the formulation. The active ingredient 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is obtained in the form of an emulsion, while the active ingredient 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide is obtained in the form of a suspension. Both the emulsion and suspension are then contacted with agronomically acceptable excipients to ultimately form the formulations of the present disclosure.

Process for preparing 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide emulsion (oil phase)

Accurately weigh 300 grams/liter of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide (equivalent to 28.5% w/w of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide compound per 100% w/w) and add to the beaker. To the beaker is added a suitable amount of an aromatic hydrocarbon solvent alone or a fatty acid based on dimethylamide or a mixture of both. This mixture was prepared for a1 liter batch of SE formulation. It was stirred well at 300rpm for 30 minutes at ambient temperature using an IKA RW28 stirrer and then the surfactant of the emulsion phase was added as mentioned in table 1. The resulting mixture was stirred again until the solution became clear and homogeneous.

Preparation method of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide suspension (suspension phase)

200 grams/liter of 2',4' -dichloro-5 '- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide (equivalent to 17.5% w/w per 100% w/w of 2',4 '-dichloro-5' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide compound) was accurately weighed and added to a beaker to form a total of 1 liter batches of SE formulation. To the beaker was added one or more of the surfactants of the suspension phase, including modified sodium lignosulfonate and acidic buffer, followed by an antifreeze, antifoam and distilled water as the continuous phase, as mentioned in table 1. The resulting mixture is thoroughly stirred in an IKAT18 high shear mixer or by any suitable high shear mixer and then run through a wet milling apparatus 0.35L laboratory mill at 3000rpm for about 15 minutes at 10 ℃. Milling was continued until 90% of the particles became 5 microns in size (d 90).

Method for bringing together an oil phase and a suspension

The suspension phase was removed from the wet milling equipment and added to a moderate shear mechanical IKA RW28 mixer. The stirring speed was maintained at 300rpm at ambient temperature while the emulsion phase was slowly added to the mixer. After the emulsion phase was completely added, stirring was continued for another 20 minutes, then the thickener, biocide and acidic buffer were added as mentioned in table 1. The resulting mixture was further stirred in a brookfield viscometer DVII + Pro at 300rpm using spindle 3 at 30 ℃ for 45 minutes until a viscosity in the range of about 250-400cps was reached. The desired viscosity is adjusted by adding more water or thickening and the mixture is again stirred at a speed of about 300rpm for another 30 minutes.

Table 1 describes 3 pre-mix formulations, labelled from a to C, prepared with different weight percentages of the above mentioned classes of components. The table also includes the percentage of active ingredient content before (day 0) and after 14 days of accelerated storage and an analysis of it in terms of percentage degradation compared to the% degradation allowed. The initial and final% of the 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide content before and after accelerated storage over the time periods mentioned were calculated. The storage stability of the pre-mix formulations of the present disclosure was compared to the storage stability of the combination with a tank mix. The term tank mix means that the specific active ingredients of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide are now mixed in a tank prior to spraying. According to standard international specifications, 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide can be regarded as stable at a maximum of 5% degradation.

Table 1:

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table 1 shows that there is a significant difference in accelerated storage stability at different wt% of certain components in the pre-mixed formulation. 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide were determined using High Performance Liquid Chromatography (HPLC) analytical techniques. The key is the wt% of the various components added in the pre-mix formulation. Since the solvent of 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide plays an important role in determining its stability, all three pre-mixed formulations were further tested with respect to storage stability. The pre-mix formulations were checked for viscosity, pourability and dispersion stability and compared to standard specifications. In table 1, the formulation contains sulfentrazone pretilachlor, which is 17.5%:28.5% se (about 1.625) and is the most preferred ratio range of 1:1-1:2. In another experiment, a higher ratio of 17.5%:36.75% of sulfentrazone to pretilachlor was performed with a loading ratio of the two active ingredients outside 1:2. It was found that pretilachlor loading of more than 35% makes it suitable to consume more continuous diluent water to keep it in stability and at the same time consume more surface active compounds like EO-PO (ethylene oxide and propylene oxide) block copolymers and yet another polymeric surfactant. This increase in the amount of vehicle affects the balance between the pretilachlor emulsion phase and the sulfentrazone suspension phase and makes them less stable physico-chemically. Thus, a penoxsulam to pretilachlor ratio of 1:1-1:2 is preferred and in a higher ratio range suspoemulsions were found to result in less stable formulations.

Table 1A shows data collected for viscosity in cps at 30 ℃, pourability in percent of maximum residue, and dispersion stability in volume of deposit obtained (in milliliters). Data were recorded at day 0 and Accelerated Storage Test (AST) and the percent increase in each property was calculated. Table 1A also includes the method used for each test.

Table 1A:

the results and observations in table 1A show that all three pre-mix formulations A, B and C give comparable results. The pre-mix formulation and method of preparation thereof according to the present disclosure stabilizes the 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide active ingredient content as showing no significant changes in physical and chemical properties, i.e. appearance, active ingredient content, viscosity, pourability and dispersion stability and thus being useful for further application.

Example 2

Field test on clay loam

Table 2 discloses details of 10 treatments for field trials in a field transplanted with rice. Details of the treatment (dose g a.i./ha and formulation dose/ha) are given in table 2. The application time for all treatments was within 0-3 days after transplantation. Treatments T3 to T7 were sown in the field, whereas T8-T9 were applied by spraying with branches and leaves.

Table 2:

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the experiment was performed in example 2 using ten treatments as described above. The performance of the new combination of the active ingredient 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide + 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide 500SE formulation against the weeds system in rice crops in the autumn crop season was evaluated. The recommended set of practices for rice crops is followed to increase the crop. Treatment was applied in a pre-emergence spray on the next day of transplantation (DAT). Phytotoxic treatments were performed on a scale of 1-10 for all treatments. To assess the plant health of rice crops, yield attribute parameters such as number of tillers per hole, plant height, rice yield and straw yield were recorded at various appropriate time intervals. Data on the population of weeds and their dry weight were also recorded. The results of several quantitative and qualitative studies are listed in tables 3 to 14 below.

The present disclosure will now be explained in more detail, illustrating but not intended to be limiting thereof.

Field test-1

A field trial was performed on an Angstrom Lu Lu, andelant, india, with clay loam seeded with rice of the MPU 1121 variety. The plot size is 10m × 10m (100 square meters). Treatments T3 to T10 were mixed with 1.25kg of a carrier selected from sand or urea, which was applied as a pre-emergence application the following day after transplantation.

Example 3

Phytotoxicity study (preemergence control of weeds)

Phytotoxicity observations (if any) were recorded for all treatments at day 3, day 15 and day 30 post-transplant as reported in tables 3-8. The symbol and grade used to document phytotoxicity is the nature of the lesion: she Sunshang (l); withering (w); pulse condition (v); necrosis (n); upward (e) and downward (h). These grades are on a scale of 1-10 according to the CIB protocol, where a scale of 1-10 represents the range of percent phytotoxicity: 1=0% -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%.

Table 3 shows the symptoms of She Sunshang (l) on a scale of 1-10 at different time intervals before and after treatment administration. All treatments did not show any symptoms of leaf damage and showed 0% leaf damage at all stages of the rice crop.

Table 3:

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* The recorded phytotoxicity observations of leaf lesions were 0% and therefore graded as l-1

Table 4 shows symptoms of wilting (w) before and after application of the treatment on a scale of 1-10. None of the treatments showed any symptoms of wilting and 0% wilting was recorded at all stages of the rice crop.

Table 4:

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* The phytotoxicity observations reported for wilting were 0% and therefore rated as w-1

Table 5 shows the symptoms of pulse conditions (v) on a scale of 1-10 before and after the treatment was applied. All treatments did not show any pulse-brightness symptoms and 0% pulse-brightness was recorded at all stages of the rice crop.

Table 5:

* The recorded phytotoxicity observations of pulse are 0% and are therefore graded as v-1

Table 6 shows the symptoms of necrosis (n) on a scale of 1-10 before and after the treatment was administered. All treatments did not show any symptoms of necrosis and 0% necrosis was recorded at all stages of the rice crop.

Table 6:

* The phytotoxicity observations of the necrosis recorded were 0% and thus graded as n-1

Table 7 shows symptoms of epinasty (e) on a scale of 1-10 before and after the treatment was administered. None of the treatments showed signs of epinasty and 0% epinasty was recorded at all stages of the rice crop.

Table 7:

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* The recorded epinasty phytotoxicity observations were 0% and therefore ranked as e-1

Table 8 shows symptoms of downward sex (h) on a scale of 1-10 before and after the treatment was administered. All treatments did not show any symptoms of downward bias and 0% downward bias was recorded at all stages of the rice crop.

Table 8:

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* The reported downward phytotoxicity observation was 0% and was therefore graded as h-1

Tables 3 to 8 show that all treatments did not show any phytotoxic symptoms and 0% of symptoms in terms of leaf damage, wilting, veining, necrosis, epinasty and hyponasty were recorded at all stages of the rice crop.

Example 4

Analysis of biometric parameters

The biometric parameters in terms of tiller number (Table 9), plant height (Table 10), rice yield and straw yield (Table 11) were recorded

The same repeats of R1, R2 and R3 as used in example 4 were employed. Statistical analysis was performed on the data to compare the treatments. For convenience, the volume of the administered dose for all treatments is already included in the table.

Table 9 discloses the number of tillers per hole observed at day 30 and day 60 post-transplant with each treatment applied. Observations were recorded in 3 replicates of each treatment. The average number of tillers observed after application treatments T3 to T10 was compared with the average number of tillers observed when the treatments T2 were manually herbicidal. Statistical analysis of the entire data was performed.

Table 9:

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the results and observations in table 9 show that there was no significant difference between these treatments in tiller number per hole among all observations recorded. The tillering number of all treatments was comparable to hand-herbicidal plots, but clearly more advantageous than the weed check treatment T1.

Table 10 discloses the effect of each treatment on the height of rice plants observed at day 30 and day 60 after transplantation. The average height of all herbicide treated plants was comparable to the manual weeding treatment and was more advantageous than the weed inspection treatment.

Table 10:

table 11 discloses the effect of each treatment on rice yield (kg/ha) and straw yield (kg/ha) of the rice crop recorded at harvest.

Table 11:

the highest rice and straw yields were recorded for the manual weeding treatment (T2). The treatments of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide were 230+345g a.i./ha and 250+375g a.i./ha, respectively, with the highest rice and straw yields among herbicide treatments. These treatments were statistically comparable to manual herbicidal treatments. These treatments are more advantageous when compared to standard herbicide treatments.

Example 5

Observation of weed control and weed flora

Observations were recorded for weed population/square meter and dry weight of weeds (in grams) per square meter at 30, 45, 60 and 75 days of transplantation (DAT), as recorded in table 12. Statistical analysis was performed on the data.

Table 12:

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the data in table 12 show that treatments T5 and T6 recorded the lowest number of weeds per square meter and were comparable to the manual herbicidal treatment. These treatments are more advantageous when compared to all other treatments and all standard treatments in all observations recorded. The dry weight of the weeds showed a similar trend of results.

Table 13 discloses the specific weeds observed after application of the treatment, which were identified, counted and recorded as follows. The observation result is carried out on weeds like broadleaf weeds, such as eclipta prostrata, ludwigia tenuifolia and monochoria vaginalis. Gramineous plants like cilostachys barnyard, paspalum, and sedge, cyperus heterophyllus, cyperus rotundus and scirpus yagara.

Table 13:

the contents of Table 13 clearly show the effectiveness of the treatments T5 and T6 in controlling a broad spectrum of weed flora in rice crops. It was observed that the efficacy of the treatment increased from T5 to T6, as the volume of the dose increased. Treatment of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide + 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide 500SE gave a more advantageous control of cyperus rotundus when compared to standard treatment. The overall quantitative analysis of the data shows that the innovative combination of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonylaniline 200+ 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide 300 500SE g/L formulations at 230+345g a.i./ha and 250+375g a.i./ha are the best treatments in herbicide treatment and are comparable to each other in effectively controlling a broad spectrum of grasses, broadleaf weeds and sedges.

Table 14 shows the dry weight (in g)/square meter recorded for each weed species as in table 13.

Table 14:

the dry weight of the weeds showed a tendency of results similar to the number of weeds. From the analysis of the above data it can be concluded that a herbicide composition/formulation comprising a combination of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide 200+ 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide 300g/L SE formulation applied as a pre-emergence herbicide in clay soil at 230+345g a.i./ha and 250+375g a.i./ha, respectively, is comparable to and more dominant and longer lasting than all other herbicide treatments in broad spectrum control of weeds and without causing significant phytotoxicity to the crop. The formulation also achieves the desired results of high rice and straw yields, maximum tillering numbers and minimal weed population and dry weight. Furthermore, the herbicidal compositions/formulations treated as suspoemulsions of the present disclosure effectively exhibit desirable storage stability and effective methods of preparation and application thereof.

Field test-2

The field trials for transplanting rice fields were performed on endo-loper of indian andela bang with clay loam seeded with rice of the NLR-34449 variety. The plot size was 10m × 20m (200 square meters). Treatments T3 to T10 were mixed with 2.0kg of a carrier selected from sand or urea, which was applied as a pre-emergence application the following day after transplantation.

Example 6

Phytotoxicity Studies (preemergence control of weeds)

Phytotoxicity observations (if any) were recorded for all treatments at day 3, day 15 and day 30 post-transplant. The sign and grading used to document phytotoxicity is a property of the lesion: she Sunshang (l); withering (w); pulse (v); necrosis (n); upward (e) and downward (h). These classifications are according to the CIB protocol, where 1=0% -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%.

Table 15 shows the symptoms of She Sunshang (l) on a scale of 1-10 at different time intervals before and after treatment was administered. All treatments did not show any symptoms of leaf damage and 0% leaf damage was recorded at all stages of the rice crop.

Table 15:

* The phytotoxicity observations recorded for leaf lesions were 0% and therefore graded as l-1

Table 16 shows the symptoms of wilting (w) on a scale of 1-10 before and after treatment was applied. None of the treatments showed any symptoms of wilting, 0% wilting was recorded at all stages of the rice crop.

Table 16:

Table 17 shows the symptoms of pulse oximes (v) on a scale of 1-10 before and after treatment was administered. All treatments did not show any pulse condition and 0% pulse was recorded at all stages of the rice crop.

Table 17:

Table 18 shows the symptoms of necrosis (n) on a scale of 1-10 before and after the treatment was administered. All treatments did not show any symptoms of necrosis and 0% necrosis was recorded at all stages of the rice crop.

Table 18:

Table 19 shows symptoms of epinasty (e) on a scale of 1-10 before and after treatment was administered. None of the treatments showed any epinasty symptoms and 0% epinasty was recorded at all stages of the rice crop.

Table 19:

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* The recorded epinasty phytotoxicity observations were 0% and therefore graded as e-1

Table 20 shows symptoms of downward sex (h) on a scale of 1-10 before and after treatment was administered. None of the treatments showed any symptoms of decentration and 0% decentration was recorded at all stages of the rice crop.

Table 20:

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Tables 15 to 20 show that all treatments did not show any phytotoxic symptoms and 0% of symptoms in terms of leaf damage, wilting, pulse clarity, necrosis, epinasty and infranasty were recorded at all stages of the crop.

Example 7

Analysis of biometric parameters

The biometric parameters in terms of tiller number (table 21), plant height (table 22), rice yield and straw yield (table 23) were recorded. Statistical analysis ANOVA was performed on the data.

Table 21 shows the data for the number of tillers observed for each treatment. There was no significant difference between the mean values of tillering numbers recorded at 30DAT and 60DAT in the herbicide treatments (T3 to T10). These treatments are comparable to the manual weeding treatment (T2) and are more advantageous than the weed inspection treatment (T1).

Table 21:

table 22 records data on the plant heights observed at different time intervals. In table 21, a similar trend in plant height and tiller number was observed as a result.

Table 22:

thus, different doses of 500SE formulation 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonylaniline 200+ 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide were found to be effective in maintaining plant height in rice crops.

Table 23 shows the rice and straw yields recorded at harvest. The average of all replicates of each treatment was calculated and compared to the standard treatment.

Table 23:

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the highest rice and straw yields were recorded for the manual weeding treatment (T2). The treatments of 500SE formulation 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide were 230+345g a.i./ha and 250+375g a.i./ha, respectively, with the highest rice and straw yields among herbicide treatments. These treatments were statistically comparable to manual herbicidal treatments. These treatments are more advantageous when compared to standard herbicide treatments.

Example 8

Observation of weed control and weed flora

Table 24:

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table 24 shows that the manual herbicidal treatment (T2) recorded the lowest number of weeds among all observations. Treatments of &5 and T6 at 230+345g a.i./h and 250+375g a.i./ha recorded the lowest number of weeds and these treatments were statistically comparable to the manual weeding treatments. These processes have advantages over standard processes. The dry weight of the weeds showed a similar trend of results as the number of weeds (table 24).

Table 25 discloses the specific weeds observed after application of the treatment, which were identified, counted and recorded as follows.

Table 25:

the contents of table 25 show the effect of treatment on the number of weeds and the dry weight of the weed species. Treatments 230+345g a.i./ha and 250+375g a.i./ha recorded the lowest number of weeds and were comparable to the manual weeding treatment. These treatments are more advantageous when compared to standard treatments. It is interesting to note that the treatment of 500SE formulation 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide was more advantageous in recording the lowest amount of Cyperus rotundus when compared to the standard treatment.

The dry weight of the weeds showed a similar trend in results to the number of weed species, as recorded in table 26.

Table 26:

example 9

Test on sandy loam

Another test was performed in sandy loam in Goodrolol, tamilnado. Lower doses of the 500SE formulation 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide + 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide were evaluated in transplanted rice due to low adsorption of the herbicide and faster release of chemicals when compared to clay loam. Details of the processing are contained in table 27. These formulations were prepared using the methods described above.

Table 27:

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field test-3

A field trial of transplanting rice fields was performed on goodlol located in taimilner bang, india with sandy loam seeded with rice of PY 3 variety. The plot size was 10m × 10m (100 square meters). Treatments T3 to T10 were mixed with sand or urea and applied as pre-emergence on the second day after transplantation and sown in field ponding.

Example 10

Phytotoxicity Studies (preemergence control of weeds)

Phytotoxicity observations (if any) were recorded for all treatments before day 3, day 15 and day 30 post-transplantation. The sign and grading used to document phytotoxicity is a property of the lesion: she Sunshang (l); withering (w); pulse (v); necrosis (n); upward (e) and downward (h). These classifications are according to the CIB protocol, where 1=0% -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%.

Table 28 shows symptoms of She Sunshang (l) on a scale of 1-10 at different time intervals before and after treatment was administered. All treatments did not show any symptoms of leaf damage and 0% leaf damage was recorded at all stages of the rice crop.

Table 28:

Table 29 shows symptoms of wilting (w) on a scale of 1-10 before and after treatment was applied. None of the treatments showed any symptoms of wilting and 0% wilting was recorded at all stages of the rice crop.

Table 29:

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Table 30 shows the symptoms of pulse oximes (v) on a scale of 1-10 before and after treatment was administered. All treatments did not show any pulse condition and 0% pulse was recorded at all stages of the rice crop.

Table 30:

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Table 31 shows the symptoms of necrosis (n) on a scale of 1-10 before and after the treatment was administered. All treatments did not show any symptoms of necrosis and 0% necrosis was recorded at all stages of the rice crop.

Table 31:

* The phytotoxicity observations of the necrosis recorded were 0% and therefore graded as n-1

Table 32 shows symptoms of epinasty (e) on a scale of 1-10 before and after treatment was administered. None of the treatments showed any symptoms of epinasty and 0% epinasty was recorded at all stages of the rice crop.

Table 32:

Table 33 shows symptoms of downward sex (h) on a scale of 1-10 before and after treatment was administered. None of the treatments showed any symptoms of decentration and 0% decentration was recorded at all stages of the rice crop.

Table 33:

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Tables 28 to 33 show that all treatments did not show any phytotoxic symptoms and 0% of symptoms in terms of leaf damage, wilting, pulse clarity, necrosis, epinasty and infranasty were recorded at all stages of the crop.

Example 11

Analysis of biometric parameters

The adsorption of pre-emergence herbicides into soil is higher in clay loam when compared to sandy loam. In this context, herbicide compositions are evaluated at lower doses. And recording the observed results of tillering number, plant height and rice and straw yield. Observations of the weed flora, number of weeds per square meter and dry weight of weeds were recorded at periodic intervals.

There was no significant difference between these herbicide treatments in the number of tillers per hole. These treatments were comparable to manual weeding treatments and were more advantageous than weed control treatments (table 34).

Table 34:

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observations of the height of the plants showed a trend of results similar to the number of tillers (table 35).

Table 35:

the highest rice and straw yields were recorded for the manual weeding treatment (T2) (table 36). In the herbicide treatment, 500SE formulation 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonylaniline at 150+225g a.i./ha and 170+255g a.i./ha recorded the highest yield of rice and straw and was comparable to the manual herbicidal treatment. These treatments are more advantageous when compared to standard treatments.

Table 36:

example 12

Observation of weed control and weed plot

The number of weeds per square meter and the dry weight of the weeds were monitored at 30, 45, 60 and 75 days of transplantation (DAT), as noted in table 37. Species, number of weeds per square meter and dry weight of weeds were recorded to obtain a better understanding of the efficacy of these treatments on the weed spectrum. Statistical analysis was also performed on the data.

Table 37:

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the manual weeding treatment recorded the lowest number of weeds. The treatment of the 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide + 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide 500SE formulation at the ratios tested recorded the lowest number of weeds and these treatments were comparable to the standard treatments. The number of weeds in the combined treatment was significantly less when compared to the individual treatments. This clearly shows the synergistic effect of the combined preparation. Treatment of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide + 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide SE 500 formulation at 150+225g a.i./ha and 170+255g a.i./ha was found to be more advantageous in weed control. These treatments provide control of longer duration when compared to standard treatments.

The dry weight of the weeds showed a similar trend of results when compared to the number of weeds per square meter (table 37). Table 38 and table 39 give the species counts per square meter of the number of weeds and the observations of the dry weight of the weeds, respectively.

Table 38:

treatment of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide + 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide 500SE formulation at 150+225g a.i./ha, 170+255g a.i./ha, and 190+285g a.i./ha recorded the least weeds when compared to standard treatment. It is interesting to note that these treatments are clearly more advantageous in the control of sedges when compared to the standard treatments (table 38). The dry weight of the weeds showed similar trends in results (table 39).

Table 39:

based on the results of the study in Table 39, it can be concluded that the 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide + 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide 500SE formulation at 150+225g a.i./ha and 170+255g a.i./ha is not phytotoxic to crops at all stages. They are more advantageous in weed control and provide longer duration control when compared to standard treatments.

Example 13

In the above examples, the selected solvents were used in the preparation of the suspoemulsion. Further experiments were performed to optimize the preparation of suspoemulsions with water as solvent. It was found that by partially or totally replacing one or more organic solvents with water and a suitable surfactant, the pretilachlor EW phase gave better results. It not only has better physicochemical properties, but also is found to be a safer, easy to use, environmentally friendly formulation since it does not contain any petroleum hydrocarbon solvents.

To further illustrate, the following experiments as provided in table 40 were performed and an analysis of the resulting suspoemulsions was performed.

Watch 40

Experiments 72 to 75 produced 1ml sediment, 1ml emulsion, with a top layer of syneresis. However, experiment 76, which had water in the pretilachlor (pretichlor) emulsion phase, passed both physical appearance and dispersion stability. The dispersion stability test is directly related to the appearance of the product when sprayed by the farmer in the field and in this test the formulation may be less desirable if any emulsions or deposits are formed.

Experiment 76, in which pretilachlor was formulated into EW with water only, was considered a more advantageous performance and was further tested by incorporating an additional dispersant as a co-dispersant (which is a polymer as mentioned in Table 41) in the sulfentrazone suspension phase

It was also found that this additional dispersant as shown in table 41 provides stability to the formulation, stabilizing not only the active ingredient stability but also the actual dilution characteristics like dispersion stability.

Since this polymer protects the stability of the active ingredient, no acidic buffer is needed and its use is stopped.

Table 41

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Experiments 77 to 80 were performed with various surfactants and compared physical appearance, dispersion stability and top layer syneresis. As can be observed from table 41, experiments 78, 79 and 80 were found to be promising, and in order to determine the reproducibility and reproducibility of the results, the following experiments 95 to 98 were performed, as described in table 42.

Watch 42

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ND-not determined

It is clear from table 42 that the formulations corresponding to experiments 96 and 98 have minimal or no top layer syneresis and better dispersion stability compared to experiments 95 and 97. Thus, the formulation with the polymer ultrazine NA gave better stability and the formulation was used for further screening. Experiments 96 and 98 were repeated in large scale production and the results are listed in table 43 below.

Watch 43

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Table 43 clearly shows better physical properties and has good dispersion stability and appearance. These results show that these formulations are stable, can be prepared on a large scale and are effectively reproducible.

When the CIPAC test procedure was used to evaluate other physical properties specified for the SE formulation (suspoemulsion) in accordance with the FAO specification, it was found that the polymer Ultrazine NA provided additional stability to the formulation, as performed in experiment 105, as shown in table 43.

The same experiment 105, (sulfentrazone 200+ pretilachlor 300 SE) was sent to a number of indoor field trials and field trials conducted at agricultural research institutes in different regions.

Example 14

Field test biological efficacy data:

field trials were conducted at three sites, namely, angstrom Lu Luhe naloxone at andela, india and goodalol at tamira, to evaluate the biological efficacy of the formulations for weed suppression and to optimize the appropriate herbicide compositions/formulations and their effect on transplanted rice under various soil conditions. Different varieties were used to see if there were any variety differences. Rice crops are grown using a normal set of practices under field conditions in their respective areas, like fertilizing, pest control, watering and other farming practices, to ensure good growth of the crop until harvest.

Study of the field trials (Angstrom Lu Lu) -formulations 77 to 80

In the first batch, premixed samples of experiment 77, experiment 78, experiment 79 and experiment 80 were evaluated with 17 treatments in angstroms Lu Lu of andela. These treatments were repeated three times to record phytotoxicity observations, tillering number/plant, plant height, weed density and biomass, and yield parameters. These treatments were applied once, the next day after transplantation. The treatments of these samples were mixed in the required amount of sand or urea and spread on a paddy field with water accumulation. The treatment of pretilachlor, penoxsulam, and combinations thereof is applied in a carpet leaf pre-emergence application. For each treatment, an appropriate amount of area of the treated plot was made to achieve the desired application rate based on the unit area of the calculated and measured application. The sand or urea required to treat the desired area is collected. The required amount of the formulation is mixed well with sand or urea and spread in the field in the water. By this method, the contact of chemicals with the branches and leaves is minimized. Treatments were rated and compared to manual herbicidal treatment (no weeds), weed check (water spray) and standard herbicide treatment (commercially popular and recommended).

Table 44 illustrates treatment with various formulations including the formulations of experiments 77 to 80 (T3 to T14) and standard herbicide compositions (T15 to T17). These formulations were applied within 0-3 days after the number of transplantation days by sowing with urea or by spraying through the branches and leaves.

Watch 44

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Phytotoxicity study

Phytotoxicity observations (if any) were recorded for all treatments on day 3, day 15 and day 30 post-transplant as reported in tables 45-50. The symbol and grade used to document phytotoxicity is the nature of the lesion: she Sunshang (l); withering (w); pulse condition (v); necrosis (n); upward (e) and downward (h). These grades are on a scale of 1-10 according to the CIB protocol, where a scale of 1-10 represents the range of percent phytotoxicity: 1=0% -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%.

TABLE 45

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The phytotoxicity observations recorded for leaf lesions were 0% and therefore graded as L-1

Table 46 shows the symptoms of wilting before and after spraying sulfentrazone 200+ pretilachlor 300 SE.

TABLE 46

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The phytotoxicity observations recorded for wilting were 0% and therefore graded as W-1.

Table 47 shows the symptoms of the pulse before and after spraying sulfentrazone 200+ pretilachlor 300 SE. The recorded phytotoxicity observations of pulse are 0% and are therefore rated as V-1

Watch 47

Table 48 shows symptoms of necrosis before and after spraying sulfentrazone 200+ pretilachlor 300 SE. The phytotoxicity observations of the necrosis recorded were 0% and thus graded as N-1.

Watch 48

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Table 49 shows symptoms of pre-and post-emergence of sulfentrazone 200+ pretilachlor 300SE spray. The recorded epinasty phytotoxicity observations were 0% and therefore ranked as E-1.

Watch 49

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Table 50 shows the symptoms of pre-and post-paresis of sulfentrazone 200+ pretilachlor 300SE spray. The recorded downward phytotoxicity observations were 0% and therefore ranked as h-1.

Watch 50

Analysis of biometric parameters

The biometric parameters in terms of tiller number (table 51), plant height (table 52), number of weeds and dry weeds (table 53), rice yield and straw yield (table 54) were recorded

Statistical analysis was performed on the data to compare the treatments. For convenience, the volume of the administered dose for all treatments is already included in the table.

Table 51 discloses the number of tillers per hole observed at day 30 and day 60 post-transplant with each treatment applied. Observations were recorded in 3 replicates of each treatment. The average number of tillers observed after the application treatments T3 to T17 was compared with the average number of tillers observed when the manual weeding treatment T2 was performed. Statistical analysis of the entire data was performed.

Watch 51

Table 52

Watch 53

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Watch 54

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The following observations and conclusions are drawn from the above tables 45 to 54.

All treatments did not show any phytotoxicity and showed phytotoxicity symptoms of 0% at all stages of the crop in terms of leaf damage, wilting, pulse brightness, necrosis, superior and inferior symptoms. Therefore, it is recorded under category 1 (tables 45 to 50). In all observations recorded, there was no significant difference between these herbicide treatments in tiller number per hole (table 51). The tillering number of all herbicide treatments was comparable to that of hand-herbicidal plots, but clearly more advantageous than the weed check treatments.

The height of the plants encoding the product experiments 78, 79 and 80 was comparable to the standard treatment and the manual weeding treatment at all doses tested in all observations recorded (table 52). In the herbicide treatment, experiment 77 recorded the lowest plant height, but higher than the weed check treatment.

The main weed area in the weed inspection land is broad-leaved weeds including dayflower, eclipta prostrata, ludwigia tenuissima, duckweed and monochoria vaginalis, gramineous plants such as cilaria verrucosa, paspalum leptochloa and cyperus rotundus, cyperus rotundus and scirpus indica

The treatments of the sulfentrazone + pretilachlor 500SE formulations of experiments 78, 79 and 80 recorded the lowest number of weeds at all doses tested and were comparable to the manual herbicidal treatment (table 53). The treatment of sulfentrazone + pretilachlor 500SE at 230+345g a.i./ha and 250+375g a.i./ha was higher and comparable to the standard treatment, and comparable to the manual weeding treatment.

The dry weight of the weeds showed similar trends in results (table 53). Treatment with the formulations of sulfentrazone + pretilachlor 500SE at 250+375g a.i./ha and 230+345g a.i./ha experiment 78, 79 and experiment 80 provided longer duration of control when compared to standard herbicide treatment.

Treatment of sulfentrazone + pretilachlor 500SE at 250+375g a.i./ha and 230+345g a.i./ha recorded the lowest number of weeds in the overall weed spectrum. It is interesting to note that these treatments provided excellent control of sedges when compared to the standard treatments (table 53). The results clearly show that the control of cyperus rotundus by sulfentrazone + pretilachlor is advantageous and has a longer duration of control. Treatment of the sulfentrazone + pretilachlor 500SE formulations of experiments 78, 79 and 80 recorded the lowest number of weeds across the weed spectrum and appeared to be promising in clay loam.

Based on the above study results it was concluded that experiments 78, 79 and 80 have better performance and are comparable to manual herbicidal treatment in terms of broad spectrum weed (number and dry weight of weeds) and rice and straw yield compared to the formulation of experiment 77, all standard herbicide treatments of sulfentrazone + pretilachlor 500SE at all ratios of the experiments, respectively. These treatments provide longer duration control when compared to standard herbicide treatments.

FieldExperimental studies (Goodrolol) -preparations 77 to 80

In the first batch, premixed samples of experiment 77, experiment 78, experiment 79 and experiment 80 were evaluated in goodlole, tamirand, with 17 treatments. These treatments were repeated three times to record phytotoxicity observations, tillering number/plant, plant height, weed density and biomass, and yield parameters. These treatments were applied once, the next day after transplantation. The treatments of these samples were mixed in the required amount of sand or urea and spread on a paddy field with water accumulation. The treatment of pretilachlor, penoxsulam and combinations thereof is applied in a carpet pre-emergence application. For each treatment, an appropriate amount of area of the treated plot was made to achieve the desired application rate based on the unit area of the calculated and measured application. The sand or urea required for the treatment of the desired area is collected. The required amount of the formulation is mixed well with sand or urea and spread in the field in the water. By this method, the contact of chemicals with the branches and leaves is minimized. Treatments were rated and compared to manual herbicidal treatment (no weeds), weed check (water spray) and standard herbicide treatment (commercially popular and recommended).

Table 55 illustrates treatment with various formulations including the formulations of experiments 77 to 80 (T3 to T14) and standard herbicide compositions (T15 to T17). These formulations were applied within 0-3 days after the number of transplantation days by sowing with urea or by spraying through the branches and leaves.

Watch 55

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Phytotoxicity study

Phytotoxicity observations (if any) were recorded for all treatments on day 3, day 15 and day 30 post-transplant and are recorded in tables 56-61. The sign and grading used to document phytotoxicity is a property of the lesion: she Sunshang (l); withering (w); pulse (v); necrosis (n); superiority (e) and inferiority (h). These grades are on a scale of 1-10 according to the CIB protocol, where a scale of 1-10 represents the range of percent phytotoxicity: 1=0% -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%.

Watch 56

Table 57 shows symptoms of wilting before and after spraying sulfentrazone 200+ pretilachlor 300 SE.

Watch 57

The phytotoxicity observations of the wilt recorded were 0% and therefore graded as W-1.

Table 58 shows the symptoms of clear pulse before and after spraying sulfentrazone 200+ pretilachlor 300 SE. The recorded phytotoxicity observations of pulse brightness were 0% and therefore graded as V-1

Watch 58

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Table 59 shows symptoms of necrosis before and after spraying sulfentrazone 200+ pretilachlor 300 SE. The phytotoxicity observations of the necrosis recorded were 0% and thus graded as n-1.

Watch 59

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Table 60 shows the symptoms of pre-and post-spray topsides of sulfentrazone 200+ pretilachlor 300 SE. The recorded epinasty phytotoxicity observations were 0% and therefore ranked as E-1.

Watch 60

Table 61 shows the symptoms of pre-and post-paresis of sulfentrazone 200+ pretilachlor 300SE spray. The reported downward phytotoxicity observation was 0% and was therefore ranked as h-1.

Watch 61

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The field trial study showed that all treatments did not show any phytotoxicity and showed phytotoxicity symptoms of 0% at all stages of the crop in terms of leaf damage, wilting, veining, necrosis, superior and inferior symptoms.

Analysis of biometric parameters

The biometric parameters in terms of tiller number (table 62), plant height (table 63), number of weeds and dry weeds (table 64), rice yield and straw yield (table 65) were recorded

Table 62 discloses the number of tillers per hole observed at day 30 and day 60 post-transplant with each treatment applied. Observations were recorded in 3 replicates of each treatment. The average number of tillers observed after the application treatments T3 to T17 was compared with the average number of tillers observed when the manual weeding treatment T2 was performed. Statistical analysis of the entire data was performed.

Watch 62

Table 63

Table 64

Table 65

It was found that the results obtained from field trial studies using formulations 77 to 80 in guldolol of tamiban were consistent with the results obtained in angstroms Lu Lu of andersonia. Based on these results, formulations 78 to 80 were found to perform better than formulation 77 at all doses and all ratios. And these treatments provide better weed control and longer duration control when compared to standard herbicide treatments.

Example 15

Field trial study-formulations 96 to 98

The formulations corresponding to experiments 96 to 98 were further evaluated by field trial studies. These formulations were evaluated in angstroms Lu Lu of anderson and guldoler of tamireland with 14 treatments. These treatments were repeated three times to record phytotoxicity observations, tillering number/plant, plant height, weed density and biomass, and yield parameters. These treatments were applied once, the next day after transplantation. The treatments of these samples were mixed in the required amount of sand or urea and spread on a paddy field with water accumulation. The treatment of pretilachlor, penoxsulam and combinations thereof is applied in a carpet pre-emergence application. For each treatment, based on calculating and measuring the unit area of application, the appropriate amount of treatment plot area was established to achieve the desired application rate. The sand or urea required for the treatment of the desired area is collected. The required amount of chemical is thoroughly mixed with sand or urea and spread in the water in the field. By this method, the contact of chemicals with the branches and leaves is minimized. Treatments were rated and compared to manual herbicidal treatment (no weeds), weed check (water spray) and standard herbicide treatment (commercially popular and recommended).

Study of field trials (Angstrom Lu Lu) -formulations 96 to 98

Formulations corresponding to experiments 96 to 98 were evaluated by field trial studies. These formulations were evaluated in Angstrom Lu Lu of Androgram with 14 treatments. These treatments were repeated three times to record phytotoxicity observations, tillering number/plant, plant height, weed density, biomass and yield parameters.

Table 66 illustrates treatment with various formulations including the formulations of experiments 96 to 98 (T3 to T11) and the standard herbicide compositions (T12 to T14). These formulations were applied by sowing with urea or by spraying through the branches and leaves within 0-3 days after the number of days of transplantation.

TABLE 66

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Phytotoxicity study

Phytotoxicity observations (if any) were recorded for all treatments on day 3, day 15 and day 30 post-transplant and are recorded in tables 67 to 72. The sign and grading used to document phytotoxicity is a property of the lesion: she Sunshang (l); withering (w); pulse condition (v); necrosis (n); upward (e) and downward (h). These grades are on a scale of 1-10 according to the CIB protocol, where a scale of 1-10 represents the range of percent phytotoxicity: 1=0% -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%.

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Table 68

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* The phytotoxicity observations recorded for wilting were 0% and therefore graded as W-1

Watch 69

* The recorded phytotoxicity observations of pulse brightness were 0% and therefore graded as W-1

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Watch 72

Analysis of biometric parameters

The biometric parameters in terms of tiller number (Table 73), plant height (Table 74), number of weeds and dry weeds (Table 75), rice yield and straw yield (Table 76) were recorded

TABLE 73

Table 74

TABLE 75

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Table 76.

In all observations recorded, there was no significant difference between these herbicide treatments in tiller number per hole. The tillering numbers of all herbicide treatments were comparable to hand-herbicidal plots, but clearly more advantageous than the weed control treatments (table 73).

The height of the plants of experiment 96, experiment 97 and experiment 98 was comparable to the observations recorded at 30DAT for standard treatment and manual herbicidal treatment at all doses tested in all observations recorded. (Table 75). However, herbicide formulation experiment 97 recorded the lowest plant height in the herbicide treatment. Herbicide formulation experiments 96 and 98 recorded the highest plant heights in the herbicide treatment and these were comparable to the standard treatment.

The main weed area in the weed inspection land is broad-leaved weeds including dayflower, eclipta prostrata, ludwigia tenuissima, duckweed and monochoria vaginalis, gramineous plants such as paspalum, barnyard grass and cyperus rotundus, and sargassum flaccida and schizonepeta pratense.

The sulfentrazone + pretilachlor 500SE treatment of experiment 97 recorded the highest number of weeds in the herbicide treatment. The treatments encoding the product experiments 96 and 98 recorded the lowest number of weeds at all doses tested and were comparable to and slightly higher than the standard treatments (table 75). The dry weight of the weeds showed similar trends in results (table 75). The treatment of the encoded products of experiments 96 and 98 provided control of longer duration when compared to standard herbicide treatment.

Treatment of sulfentrazone + pretilachlor 500SE at 250+375g a.i./ha and 230+345g a.i./ha recorded the lowest number of weeds in the entire spectrum of weeds. It is interesting to note that these treatments provided excellent control of sedges when compared to the standard treatments (table 75). The results clearly show that the control of cyperus rotundus by sulfentrazone + pretilachlor is advantageous and has a longer duration of control.

The treatment of sulfentrazone + pretilachlor 500SE of experiments 96 and 98 recorded the highest rice and straw yields at all doses tested, significantly higher than experiment 97, the standard treatment and the manual weeding treatment (table 76). The treatment of sulfentrazone + pretilachlor 500SE of experiments 96 and 98 recorded the lowest number of weeds across the weed spectrum and appeared to be promising in clay loam.

Compared to the formulation of experiment 97, all standard herbicide treatments of sulfentrazone + pretilachlor 500SE at all ratios tested, respectively, the formulations of experiment 96 and experiment 98 had relatively better performance and were comparable to the manual herbicidal treatment in terms of broad spectrum weed (number and dry weight of weeds) and rice and straw yield. These treatments provide longer duration control when compared to standard herbicide treatments.

Studies on field trials (Goodrolol) -formulations 96 to 98

Formulations corresponding to experiments 96 to 98 were evaluated by field trial studies. These formulations were evaluated in guldolor of tamimer and bang with 14 treatments. These treatments were repeated three times to record phytotoxicity observations, tillering number/plant, plant height, weed density and biomass, and yield parameters.

Treatments with various formulations used in the field of angstroms Lu Lu (table 66) included formulations from experiments 96 to 98 (T3 to T11) and standard herbicide compositions (T12 to T14). These formulations were applied within 0-3 days after the number of transplantation days by sowing with urea or by spraying through the branches and leaves.

Phytotoxicity study

Observations of phytotoxicity (if any) were recorded for all treatments at day 3, day 15 and day 30 post-transplantation and the signs and grades used to record phytotoxicity are the nature of the lesions recorded in tables 77 to 82: she Sunshang (l); withering (w); pulse (v); necrosis (n); upward (e) and downward (h). These ratings are on a scale of 1-10 according to the CIB protocol, where a scale of 1-10 represents the range of percent phytotoxicity: 1=0% -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%.

Watch 77

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* The phytotoxicity observations reported for wilting were 0% and therefore graded as W-1

TABLE 79

* The recorded phytotoxicity observations of pulse are 0% and are therefore rated as V-1

Watch 80

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Table 82

Analysis of biometric parameters

The biometric parameters in terms of tiller number (table 83), plant height (table 84), number of weeds and dry weeds (table 85), rice yield and straw yield (table 86) were recorded.

Watch 83

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Watch 85

Watch 86

It was found that the results obtained from field trial studies using formulations 96 to 98 in guldolol of tamiban were consistent with the results obtained in angstroms Lu Lu of andela. Based on these results, formulations 96 and 98 were found to perform better than formulation 97 at all doses and at all ratios. And these treatments provide better weed control and longer duration control when compared to standard herbicide treatments

Example 16

Field trial study-formulations 105 and 108

Formulations corresponding to experiments 105 and 108 were similarly evaluated as described above. These samples were evaluated in Edwardroban Lu Lu and in Goldelol of Tamilnard with 11 treatments. These treatments were repeated three times to record phytotoxicity observations, tillering number/plant, plant height, weed density and biomass, and yield parameters. These treatments were applied once, the next day after transplantation. The treatments of these samples were mixed in the required amount of sand or urea and spread on a paddy field with water accumulation. The treatment of pretilachlor, penoxsulam and combinations thereof is applied in a carpet pre-emergence application. For each treatment, an appropriate amount of area of the treated plot was made to achieve the desired application rate based on the unit area of the calculated and measured application. The sand or urea required for the treatment of the desired area is collected. The required amount of chemical is thoroughly mixed with sand or urea and spread in the water in the field. By this method, the contact of chemicals with the branches and leaves is minimized. Treatments were rated and compared to manual herbicidal treatment (no weeds), weed check (water spray) and standard herbicide treatment (commercially popular and recommended).

Table 87 illustrates treatment with various formulations including the formulations of experiments 105 and 108 (T3 to T8) and standard herbicide compositions (T9 to T11). These formulations were applied by sowing with urea or by spraying through the branches and leaves within 0-3 days after the number of days of transplantation.

Watch 87

Study of field trials (Angstrom Lu Lu) -formulations 105 and 108

Phytotoxicity study

Phytotoxicity observations (if any) were recorded for all treatments (table 87) on day 3, day 15 and day 30 post-transplant and recorded in tables 88 to 93. The sign and grading used to document phytotoxicity is a property of the lesion: she Sunshang (l); withering (w); pulse (v); necrosis (n); upward (e) and downward (h). These grades are on a scale of 1-10 according to the CIB protocol, where a scale of 1-10 represents the range of percent phytotoxicity: 1=0% -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%.

Watch 88

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Watch 90

Watch 91

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Watch 93

Analysis of biometric parameters

The biometric parameters in terms of tiller number (table 94), plant height (table 95), number of weeds and dry weeds (table 96), rice yield and straw yield (table 97) were recorded.

Statistical analysis was performed on the data to compare the treatments. For convenience, the volume of the administered dose for all treatments is included in the table below.

Table 94

Watch 95

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Watch 97

In all observations recorded, there was no significant difference between these herbicide treatments in tiller number per hole. The tillering numbers of all herbicide treatments were comparable to hand-herbicidal plots, but clearly more advantageous than the weed control treatments (table 94).

The height of the plants of experiment 105 recorded the height of the lowest plants. The treatment of experiment 108 recorded the highest plant height in all observations and at different doses evaluated when compared to the standard treatment and was comparable to the standard treatment and the manual weeding treatment (table 95).

The treatment of experiment 108 recorded the lowest number of weeds at all doses tested and was comparable to the manual herbicidal treatment and slightly more advantageous than the standard treatment (table 96). The dry weight of the weeds showed similar trends in results (table 96). The treatment of experiment 105 provided control of longer duration when compared to the standard herbicide treatment and the manual weeding treatment.

Treatment of sulfentrazone + pretilachlor 500SE at 230+345g a.i./ha and 250+375g a.i./ha recorded the lowest number of weeds in the entire spectrum of weeds. It is interesting to note that these treatments provided excellent control of sedges when compared to the standard treatments (table 96). The results clearly show that the control of cyperus rotundus by sulfentrazone + pretilachlor is advantageous and has a longer duration of control.

The sulfentrazone + pretilachlor 500SE treatments of experiments 108 and 105 recorded the highest rice and straw yields and were higher than the standard treatments and the manual herbicidal treatment (table 97). The sulfentrazone + pretilachlor 500SE treatment of experiment 108 recorded the lowest number of weeds across the weed spectrum and appeared to be promising in clay loam.

Tests 108 and 105 of sulfentrazone + pretilachlor 500SE, respectively, had better performance than all standard herbicide treatments at all rates tested and were comparable to manual herbicidal treatments in terms of broad spectrum weed (number and dry weight of weeds) and rice and straw yield. These treatments provide longer duration control when compared to standard herbicide treatments.

Field trial study (Gooderoll) -formulations 105 and 108

Phytotoxicity study

Phytotoxicity observations (if any) were recorded for all treatments (table 87) at day 3, day 15 and day 30 post-transplant and recorded in tables 98 to 103. The sign and grading used to document phytotoxicity is a property of the lesion: she Sunshang (l); wilting (w); pulse (v); necrosis (n); upward (e) and downward (h). These grades are on a scale of 1-10 according to the CIB protocol, where a scale of 1-10 represents the range of percent phytotoxicity: 1=0% -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%.

Watch 98

TABLE 99

Watch 100

Watch 101

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Watch 103

Analysis of biometric parameters

The biometric parameters in terms of tiller number (table 104), plant height (table 105), number of weeds and dry weeds (table 106), rice yield and straw yield (table 107) were recorded.

Table 104

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Table 106

Table 107

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It was found that the results obtained from field trial studies using formulations 105 and 108 in guldolol of tamiban were consistent with the results obtained in angstroms Lu Lu of andela. Based on these results, formulations 105 and 108 were found to have appreciable performance, however, 105 exhibited better performance than 108. In addition, these treatments provide better weed control and longer duration control when compared to standard herbicide treatments

Example 17

Field test study-formulation 105

Formulations corresponding to experiment 105 with different sulfentrazone + pretilachlor 500SE weight ratios were further evaluated by field trial studies. These formulations were evaluated in 9 treatments in Angstrom Lu Lu of Androgram. These treatments were repeated three times to record phytotoxicity observations, tillering number/plant, plant height, weed density and biomass, and yield parameters. These treatments were applied once, the next day after transplantation. The treatments of these samples were mixed in the required amount of sand or urea and spread on a paddy field with water accumulation. The treatment of pretilachlor, penoxsulam and combinations thereof is applied in a carpet pre-emergence application. For each treatment, based on calculating and measuring the unit area of application, an appropriate amount of treatment plot area is formulated to achieve the desired application rate to collect the sand or urea needed to treat the desired area by thoroughly mixing and spreading the required amount of chemical with the sand or urea in the field's ponding to minimize chemical contact with the foliage. Treatments were rated and compared to manual herbicidal treatment (no weeds), weed check (water spray) and standard herbicide treatment (commercially popular and recommended).

Table 108 illustrates treatment with various formulations including the formulation of experiment 105 (T3 to T6) and the standard herbicide composition (T7 to T9). These formulations were applied within 0-3 days after the number of transplantation days by sowing with urea or by spraying through the branches and leaves.

Table 108

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Phytotoxicity study

Phytotoxicity observations (if any) were recorded for all treatments on day 3, day 15 and day 30 post-transplant and are recorded in tables 109 to 114. The sign and grading used to document phytotoxicity is a property of the lesion: she Sunshang (l); withering (w); pulse (v); necrosis (n); upward (e) and downward (h). These grades are on a scale of 1-10 according to the CIB protocol, where a scale of 1-10 represents the range of percent phytotoxicity: 1=0% -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%.

Watch 109

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* The phytotoxicity observations of the necrosis recorded were 0% and therefore classified as N-1

Watch 113

Watch 114

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Analysis of biometric parameters

The biometric parameters in terms of tiller number (table 115), plant height (table 116), number of weeds and dry weeds (table 117), rice yield and straw yield (table 118) were recorded.

Watch 115

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Watch 116

Table 117

Watch 118

In all observations recorded, there was no significant difference between these herbicide treatments in tiller number per hole. The tillering numbers of all herbicide treatments were comparable to hand-herbicidal plots, but clearly more advantageous than the weed control treatments (table 115).

In all observations recorded, the herbicide treatments did not differ significantly in the height of the plants and these were comparable to standard manual herbicide treatments (table 116). Weed inspection recorded the height of the lowest plants.

Of all observations recorded, the manual herbicidal treatment recorded the lowest number of weeds (table 117). Treatment of sulfentrazone 200+ pretilachlor 300SE at 200+300, 230+345 and 250+375g a.i.ha recorded the lowest weeds per unit area and these treatments were comparable to, but higher than, standard manual herbicidal treatments. Among all observations recorded, the weed test recorded the highest number of weeds. It is interesting to note that treatment with sulfentrazone 200+ pretilachlor 300SE provided superior control of sedge when compared to standard herbicide treatment (table 117). The dry weight of the weeds showed a similar trend of results.

The highest rice and straw yields were recorded for the manual weeding treatment (table 118). In herbicide treatments, sulfentrazone 200+ pretilachlor 300SE at 200+300, 230+345 and 250+375g a.i.ha recorded the highest rice and straw yields and these treatments were comparable to standard manual weeding treatments. These treatments were significantly higher than the standard herbicide treatments in terms of yield parameters.

Thus, it can be concluded that sulfentrazone 200+ pretilachlor 300SE at 200+300, 230+345 and 250+375g a.i./ha provides excellent control of weeds and longer duration of control when compared to standard herbicide treatment. These treatments were comparable to standard manual weeding treatments in terms of weed population, dry weight of weeds and thus reflected in rice and straw yield.

Example 18

Formulations comprising safeners

Within certain limits imposed by the herbicide, the plant, the method and time of application, the rate of application, and the environmental conditions, the herbicide composition is selective to a particular crop. Safeners are compounds of different chemical families which are applied together with herbicidal compositions to protect crops from damage. The use of chemical safeners provides a practical, efficient and simple method for increasing herbicide selectivity. Safeners have been successfully applied to cereal crops such as corn, rice and sorghum to combat pre-emergence thiocarbamate and chloroacetanilide herbicides. Various hypotheses have been proposed to explain the mechanism of action of herbicide safeners: interfering with the uptake and translocation of the herbicide, altering herbicide metabolism, and competing at the site of action of the herbicide. The use of herbicide safeners can greatly mitigate herbicide damage to protect crop plants and extend the field application range of existing herbicides to a wide range of crops.

Because of their phytotoxicity to crops before emergence, their use on direct-seeded or germinated or drill-seeded rice is limited. Various herbicides incorporate safeners for safe use on crops.

Thus, in the present invention, safeners selected in particular from the group consisting of fenclorim, pyrazoline, isoxadifen, clethodim or cloquintocet are evaluated for the formulation containing 17.5% + pretilachlor 28.5% SE.

Preliminary evaluations were conducted on rice, groundnut and mint crops for various safeners as tank mixes with a formulation of sulfentrazone 17.5% + pretilachlor 28.5% se. It was observed that the formulation of sulfentrazone 17.5% + pretilachlor 28.5% se with different doses of fenclorim ranging from 40 to 100g/l did not cause any phytotoxicity to the direct sown or germinated rice, transplanted rice, groundnut, potato, sugarcane and mint crops even at higher than the recommended dose.

Thus, two formulations were performed, experiments 200 and 201, a preliminary field experiment in which fenclorim was dosed with sulfentrazone 17.5% + pretilachlor 28.5% SE at 75g/l and 100 g/l.

Table 119 illustrates experiments 200 and 201 in which the safener fenclorim was included in the formulation.

Watch 119

As can be observed from table 119, the appearance and stability of the formulation was maintained using a safener. Thus, further field trial data was generated using the formulations of experiments 200 and 201.

The formulations of experiments 200 and 201 were evaluated on directly sown or germinated rice at 250+375g a.i. and 350+525g a.i./ha. These samples were compared at the same ratio with a formulation of sulfentrazone 17.5% + pretilachlor 28.5% SE. The standard used for comparison purposes was pretilachlor 50% ec, with a recommended ratio of 500g a.i./ha. The results of the study were observed to show that the formulations of experiment 200 and experiment 201 did not cause any phytotoxicity in terms of germination rate, plant height and rice yield when compared to the direct formulation.

Similarly, the formulations of experiment 200 and experiment 201 were evaluated on groundnut plants at 250+375g a.i. and 350+525g a.i./ha. These samples were compared at the same ratio with a formulation of sulfentrazone 17.5% + pretilachlor 28.5% SE. The standard used for comparison purposes was pretilachlor 50% ec, with a recommended ratio of 500g a.i./ha. The results show that the performance of the formulations of experiment 200 and experiment 201 is higher in terms of germination, plant height and yield when compared to standard treatments.

Advantages of the disclosure

The present disclosure provides a herbicidal composition/formulation which is a specific combination of the active ingredients 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide and 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide. The present disclosure provides a formulation comprising a herbicidal composition that is stable in the presence of solvents such as aromatic hydrocarbons. Furthermore, the present invention provides a water stable composition which is more advantageous in terms of its properties and agrochemical properties. Formulations with water are more user friendly and also more environmentally friendly. The herbicide composition/formulation does not cause any phytotoxicity to rice crops when applied in a specific dose as pre-emergence application in transplanted rice fields, and simultaneously shows excellent control of broad-spectrum weeds, control of longer duration and superior efficacy to sedges. The herbicide compositions/formulations of the present disclosure are suspoemulsions, provided they have a promising storage stability in terms of degradation of the highly unstable 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide. The composition/formulation was also observed to be effective on a wide range of soil types. In sandy loam, the dosage varies from 130+195g a.i./ha to 190+285g a.i./ha, and in clay loam, ranges from 190+285g a.i./ha to 250+375g a.i./ha. In addition, the herbicide compositions/formulations of the present disclosure provide improved plant health, described by increasing yield attribute parameters such as number of tillers per hole, and rice and straw yield of major crops. The present disclosure also provides an effective method of preparing a suspoemulsion herbicide composition/formulation and its application.

Field evaluation of the formulations of the present disclosure provides dose optimization, methods of application, time of application for the purpose of approval of rice and other crops in different geographical locations.

Claims

1. A herbicidal composition comprising:

(a) 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide; and

(b) 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide;

wherein the weight ratio of 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide to 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide is in the range of 1:1-1.

2. A formulation, comprising:

(a) A herbicidal composition of claim 1; and

(b) An agronomically acceptable excipient selected from the group consisting of,

wherein the weight ratio of the herbicide composition to the agronomically acceptable excipient is in the range of 40.

3. The formulation of claim 2, wherein the agronomically acceptable excipient is selected from a solvent, a surfactant, an antifreeze, an antifoam, a thickener, a biocide, a polymer, a safener, a diluent, or a combination thereof.

4. The formulation of claims 2-3, wherein the formulation comprises:

a) From 40% to 60% (w/w) of the herbicidal composition of claim 1;

b) 2% to 30% (w/w) of a solvent,

c) 2% to 10% (w/w) of a surfactant,

d) 1% to 8% (w/w) of an anti-freeze agent,

e) 0.1% to 0.5% (w/w) of an antifoaming agent,

f) 0.02% to 0.2% (w/w) of a biocide,

g) From 0.1% to 6% (w/w) of a polymer, and

h) 7% to 25% (w/w) of a diluent.

5. The formulation of claims 2-3, wherein the formulation comprises:

a) From 40% to 60% (w/w) of the herbicidal composition of claim 1;

b) 2% to 30% (w/w) water,

c) 2% to 10% (w/w) of a surfactant,

d) 1% to 8% (w/w) of an anti-freeze agent,

e) 0.1% to 0.5% (w/w) of an antifoaming agent,

f) 0.02% to 0.2% (w/w) of a biocide,

g) 0.1% to 6% (w/w) of a polymer, and

h) 7% to 25% (w/w) of a diluent.

6. The formulation of claims 4-5, wherein the surfactant is selected from butyl block copolymers, alkyl benzene sulfonates, castor oil ethoxylates, tristyrylphenol ethoxylates, sodium alkyl naphthalene sulfonate-formaldehyde condensates, acrylic acid copolymer solutions, or combinations thereof; the anti-freeze agent is selected from glycerol, propylene glycol, or a combination thereof; the antifoam is a silicone emulsion; the biocide is selected from Nipacide CI 15, proxel GXL, or a combination thereof; the polymer is a modified sodium lignosulfonate selected from Ufoxane 3A, ultrazine NA, vanisperse CB, or combinations thereof; and the diluent is water.

7. The formulation of claim 4, wherein the solvent is selected from C ₈ -C ₁₀ Dimethylamide fatty acid, C ₉ -C ₁₂ Aromatic petroleum hydrocarbons, water, or combinations thereof.

8. The formulation of claims 4-5, wherein the formulation further comprises 0.05% to 2% (w/w) of a thickening agent selected from xanthan gum, polysaccharides, cellulosic materials, hydrophilic fumed silica, hydrated magnesium silica, sodium aluminosilicate, or combinations thereof; and 6% to 12% (w/w) of a safener selected from fenclorim, mefenpyr-diethyl, isoxadifen, cloquintocet-mexyl, or a combination thereof.

9. The formulation of claims 2-8, wherein the formulation is a suspoemulsion.

10. A process for preparing the formulation of claim 2, comprising contacting the herbicidal composition of claim 1 and the agronomically acceptable excipient to obtain the formulation, wherein the weight ratio of the herbicidal composition to the agronomically acceptable excipient is in the range of 40 to 60.

11. A process for preparing the formulation of claim 4, comprising:

a) Contacting 2',4' -dichloro-5 ' - (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) methanesulfonamide with a surfactant, an antifreeze, an antifoam, a polymer, a biocide, and a diluent to form a suspension;

b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, a solvent and a diluent to form an emulsion; and

c) Mixing the suspension with the emulsion to obtain the formulation.

12. A process for preparing the formulation of claim 5, comprising:

b) Contacting 2-chloro-2 ',6' -diethyl-N- (2-propoxyethyl) acetanilide with a surfactant, water and a diluent to form an emulsion; and

c) Mixing the suspension with the emulsion to obtain the formulation.

13. The method of any one of claims 11 to 12, wherein mixing the suspension with the emulsion is optionally carried out in the presence of a thickener.

14. The method of any one of claims 11 to 12, wherein mixing the suspension with the emulsion is carried out at a stirring speed in the range of 200 to 400rpm for a time period in the range of 20 to 120 minutes.

15. The method of any one of claims 11 to 12, wherein the formulation is further mixed with a safener.

16. A method for preemergence control of a broad spectrum of weeds in a field comprising applying an effective amount of the composition of claim 1 or the formulation of any of claims 2-9.

17. A method of weed control in a crop field comprising applying the composition of claim 1 or the formulation of any one of claims 2-9 in the crop field.

18. The method of any one of claims 16-17, wherein the formulation is applied at the field rates of 0.5-1.5 liters per hectare.

19. A method as claimed in any one of claims 16 to 17, wherein the formulation is applied in the field fields to provide a total weight of the herbicidal composition in the range 100-1500g a.i./ha.

20. The method of any one of claims 16-17, wherein the formulation is applied in the fields at the time of application of the transplanted or direct seeded rice.