Patent Application
20240122183
The present invention relates to herbicidal compositions comprising of phenylpyrazoline and triazolinone compounds and at least one another herbicidal compound. More particularly, the present invention relates to a synergistic herbicidal composition comprising Pinoxaden, Carfentrazone-ethyl and at least one herbicidal compound selected from Fenoxaprop-p-ethyl or Isoproturon.
The crop protection from weeds and other vegetation which inhibit crop growth is a constantly recurring problem in agriculture. Therefore, the control of weeds or unwanted plants is economically important for the crop productivity. Researchers in the field of synthetic chemistry have produced an extensive variety of chemicals and chemical formulations as solo or combination of active ingredients for the control of such weeds or unwanted plants. Chemical herbicides of many types have been disclosed in the literature and a large number are in commercial use.
Nowadays, little seed canary grass (Phalaris minor) is a serious weed of irrigated wheat in India that has developed resistance against most of the available herbicidal control measures. In order to reduce the risk from increased number of herbicide resistant strains, mixtures of different active compounds are nowadays employed for controlling weeds or unwanted plants. By combining different active compounds having different mechanisms of action, it is possible to ensure efficient and wide spectrum control of weeds over a relatively longer period of time and preventing development of resistance. However, this requires the continued development of an effective composition with different active compounds, so as to avoid selection to the particular mechanism of action.
Therefore, there exists a need in the art to develop an herbicidal composition which is stable, synergistic, broad spectrum, environmentally safe, and more effective in control of weeds in crops. The herbicidal compositions must show a broader scope of activity to avoid or to prevent the development of resistant varieties of weeds to the active ingredients or to the mixtures of known active ingredients used by farmer while minimising the doses of chemicals sprayed in the agricultural fields.
As a solution to the above mentioned problems, the inventors of the present invention surprisingly found that composition comprising Pinoxaden, Carfentrazone-ethyl and at least one herbicidal compound selected from Fenoxaprop-p-ethyl or Isoproturon provides effective control of wide range of weeds or undesired plants.
Accordingly, the present invention provides a synergistic herbicidal composition comprising Pinoxaden, Carfentrazone-ethyl and at least one herbicidal compound selected from Fenoxaprop-p-ethyl or Isoproturon and one or more excipients.
In an embodiment, the synergistic herbicidal composition comprises of Pinoxaden in the range of 1-12.5% w/w, Carfentrazone-ethyl in the range of 1-5% w/w, and at least one herbicide compound selected from Fenoxaprop-p-ethyl in the range of 5-20% w/w and Isoproturon in the range of 40-60% w/w, and one or more excipients.
In another embodiment, the present invention provides a synergistic herbicidal composition selected from the group comprising:
In one another embodiment, the composition of the present invention is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW). In a preferred embodiment, the composition is formulated as microemulsion (ME) and wettable powder (WP).
In an embodiment, the excipient used in the present invention is selected from the group comprising of dispersing agent present in an amount in the range from 1 to 10% w/w, wetting agent is present in an amount in the range from 1 to 10% w/w, emulsifier is present in an amount in the range from 5 to 15% w/w, defoamer is present in an amount in the range from 0.1 to 5% w/w, safener is present in an amount in the range from 1 to 5% w/w, co-solvent is present in an amount in the range from 5 to 10% w/w, at least one of solvent or filler present in an amount of quantity sufficient to make 100% w/w formulation.
In another embodiment, the dispersing agent is selected from the group comprising of sodium salt of naphthalene sulphonate condensate, sulfonated aromatic polymer sodium salt, sodium polycarboxylate, ethanesulfonic acid, 2-[methyl[(9Z)-1-oxo-9-octadecenyl]amino]-sodium salt, sodium 2-(methyloleoylamino)ethane-1-sulphonate, amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, graft copolymer, salt of naphthalene sulphonate, naphthalene sulfonate formaldehyde condensate, phosphate ester, salt of polycarboxylate, alcohol block copolymer, ethoxylated polyarylphenol phosphate ester or a combination thereof. The wetting agent is selected from the group comprising of sodium lauryl sulphate, sodium alkyl naphthalene sulfonate blend, sodium alkylnaphthalenesulfonate, sodium isopropyl naphthalene sulfonate, sodium dioctylsulfosuccinate, ethoxylated polyarylphenol phosphate ester, dioctyl sulphosuccinate, non-ionic ethoxylate or a combination thereof. The emulsifier is selected from the group comprising of castor oil ethoxylate, calcium dodecylbenzene sulfonate, blend of anionic-nonionic emulsifiers, tristyryl phenol, polyalkylene oxide block copolymer, high molecular weight polymer PEG-10 PPG-5 cetyl phosphate, ethylene oxide (EO)-polyethylene oxide (PO) block copolymer, non-ionic ethoxylated emulsifier, or a combination thereof. The defoamer is selected from the group comprising of silicon emulsion, dimethyl polysiloxane emulsion, polysiloxane emulsion or a combination thereof. The safener is selected from the group comprising of AD67, benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, fenchlorazole-ethyl, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl or a combination thereof. The co-solvent is selected from the group of comprising 2-ethyl hexanol, n-butanol, dimethylsulfoxide, N-methyl-2-pyrrolidone, cyclohexanone or a combination thereof. The solvent is selected from the group comprising of naphtha, xylene, decanamide, solvent C9, water or a combination thereof. The filler is selected from the group comprising of silica and china clay or a combination thereof.
The definitions provided herein for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit, the scope of the present invention disclosed in the present disclosure.
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 the invention pertains. Although other methods and materials similar, or equivalent, to those described herein can be used in the practice of the present invention, the preferred materials and methods are described herein.
As used herein, the term “composition” or “formulation” can be used interchangeably, unless stated otherwise, is meant to encompass, and are not limited to, compositions or formulations containing the combination of Pinoxaden, Carfentrazone-ethyl and at least one herbicidal compound selected from Fenoxaprop-p-ethyl or Isoproturon or its derivative thereof.
The expression of various quantities in terms of “% w/w” or “%” means the percentage by weight, relative to the weight of the total solution or composition unless otherwise specified.
The term “active ingredient” “(a.i.)” or “active agent” used herein refers to that component of the composition responsible for control of weeds or undesired plants.
As used herein, the term “Pinoxaden” encompasses its agrochemically acceptable salt(s), derivative(s) or any other modified form of Pinoxaden. Pinoxaden belongs to the class of phenylpyrazoline herbibicide. It acts by inhibition of acetyl CoA carboxylase.
As used herein, the term “Carfentrazone-ethyl” encompasses its agrochemically acceptable salt(s), ester(s) such as Carfentrazone-ethyl, derivative(s) or any other modified form of Carfentrazone-ethyl. Carfentrazone-ethyl belongs to the class of triazolinone herbicide. It acts by inhibition of protoporphyrinogen oxidase.
As used herein, the term “Fenoxaprop-p-ethyl” encompasses its agrochemically acceptable salt(s), acids such as Fenoxaprop, Fenoxaprop-p-ethyl, derivative(s) or any other modified form of Fenoxaprop-p-ethyl. Fenoxaprop-p-ethyl belongs to the class of aryloxyphenoxypropionate. It acts by acetyl CoA carboxylase inhibition.
As used herein, the term “Isoproturon” encompasses its agrochemically acceptable salt(s), derivative(s) or any other modified form of Isoproturon. Isoproturon belongs to the class of urea herbicide. It acts by inhibition of photosystem II.
The present invention provides a composition comprising of Pinoxaden, Carfentrazone-ethyl and at least one herbicidal compound selected from Fenoxaprop-p-ethyl or Isoproturon and one or more excipients. It has been surprisingly found that the composition of the present invention not only provides effective control of weeds or undesired plants but also such combination is synergistic in nature.
The composition according to the present invention comprises of Pinoxaden in an amount in the range from 1-12.5% w/w, Carfentrazone-ethyl in an amount in the range from 1-5% w/w, and at least one herbicidal compound in the range from 5 to 60% w/w. In an aspect, at least one herbicidal compound is selected from Fenoxaprop-p-ethyl or Isoproturon. In another aspect, Fenoxaprop-p-ethyl is present in an amount in the range from 5-20% w/w. In one another aspect, Isoproturon is present in an amount in the range from 40-60% w/w.
In a preferred aspect, the composition of the present invention is selected from a group comprising of:
The composition of the present invention is formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), preferably formulated as ME and WP.
The composition of the present invention comprises of one or more excipients selected from dispersing agent, wetting agent, emulsifier, defoamer, safener, filler, solvent. In another aspect, the composition is formulated as ME and comprises of one or more excipients selected from emulsifier, safener and solvent. In one another aspect, the composition is formulated as WP and comprises of one or more excipients selected from dispersing agent, wetting agent, defoamer and filler. The composition may further comprise of other excipients as will be required in a particular type of formulation, including, but not limited to, anti-freeze agent, thickener, biocide, monomer, pH adjuster and stabilizer.
It is generally observed that solid particles in a liquid undergo spontaneous aggregation to form lumps. Hence, it is recommended to add a dispersing agent which prevents agglomeration of solid particles and keep them suspended in fluid. Accordingly, the composition of the present invention contains dispersing agent such as sodium salt of naphthalene sulphonate condensate, sulfonated aromatic polymer sodium salt, sodium polycarboxylate, ethanesulfonic acid, 2-[methyl[(9Z)-1-oxo-9-octadecenyl]amino]-sodium salt, sodium 2-(methyloleoylamino)ethane-1-sulphonate, amine salt of phosphate tristyryl phenol ethoxylated, acrylic copolymer, graft copolymer, salt of naphthalene sulphonate, naphthalene sulfonate formaldehyde condensate, phosphate ester, salt of polycarboxylate, alcohol block copolymer, ethoxylated polyarylphenol phosphate ester or a combination thereof and present in an amount in the range from 1 to 10% w/w.
Wetting is the first stage of dispersion, in which air surrounding the granular/powder composition is substituted with water. Wetting of the composition with water cannot occur if the surface tension of the liquid is very high. Hence, it is recommended to add a wetting agent to the composition to facilitate the process of dispersion of the granules/powder in the liquid. Non-limiting examples of wetting agents used herein are sodium lauryl sulphate, sodium alkyl naphthalene sulfonate blend, sodium alkylnaphthalenesulfonate, sodium isopropyl naphthalene sulfonate, sodium dioctylsulfosuccinate, ethoxylated polyarylphenol phosphate ester, dioctyl sulphosuccinate, non-ionic ethoxylate or a combination thereof and present in an amount in the range from 1 to 10% w/w.
An emulsifier is a kind of surfactant. It helps to prevent the droplets of the dispersed phase of an emulsion from flocculating or coalescing in the emulsion. It can be or include a cationic, zwitterionic or a non-ionic emulsifier. Suitable emulsifier used herein, are castor oil ethoxylate, calcium dodecylbenzene sulfonate, proprietary blend of anionic-nonionic emulsifiers, tristyryl phenol, polyalkylene oxide block copolymer, high molecular weight polymer PEG-10 PPG-5 cetyl phosphate, ethylene oxide (EO)-polyethylene oxide (PO) block copolymer, non-ionic ethoxylated emulsifier, or a combination thereof and present in an amount in the range from 5 to 15% w/w.
A defoamer is generally added to the composition, as foam formation prevents the efficient filling of a container. Suitable defoamer used herein, but not limited to, silicon emulsion, dimethyl polysiloxane emulsion, polysiloxane emulsion or a combination thereof and present in an amount in the range from 0.1 to 5% w/w.
A safener is to be understood as meaning a compound which eliminates or reduces the phytotoxic properties of herbicide in respect to useful plants, without substantially reducing the herbicidal activity against harmful plants. Non limiting examples of safeners that can be employed in present invention are AD67, benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, metcamifen, naphthalic anhydride, oroxabetrinil, or a combination thereof and is present in an amount in the range from 1 to 5% w/w.
The co-solvent used in the composition of the present invention is selected from 2-ethyl hexanol, n-butanol, dimethyl sulfoxide (DMSO), N-Methyl-2-pyrrolidone, cyclohexanone or a combination thereof and is present in an amount in the range from 5 to 10% w/w. Non limiting examples of solvents that can be employed in present invention are naphtha, xylene, decanamide, solvent C9, water or a combination thereof and is present in an amount of quantity sufficient to make 100% w/w formulation.
Other non-limiting examples of co-solvent/solvent that may be used in the present invention are alcohols such as ethanol, propanol, n-octanol, isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerine; polyol ethers such as ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ethers such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, isoparaffin, kerosene, mineral oil; aromatic hydrocarbons such as toluene, naphthalene, solvent C10, solvent C12, solvesso 100, solvesso 150, solvesso 200; chlorinated aliphatic or aromatic hydrocarbons such as chlorobenzene, chloroethylene, methylene chloride; esters such as ethyl acetate, diisopropyl phthalate, dimethyl adipate, methyl oleate, methyl tallowate; lactones such as gamma-butyrolactone; amides such as dimethylformamide, N-octylpyrolidone, N,N-dimethyldecanamide; nitriles such as acetonitrile.
A filler is added to the composition to improve the handling and storage characteristics of the composition. Fillers also add mass and/or volume to the active ingredient in order to facilitate precise measurement of the doses. Suitable fillers that may be used in the composition of the present invention include, but not limited to, bentonite clay, china clay, silica, kaolin and diatomaceous earth. The filler may be used alone or in combination and is present in an amount quantity sufficient to make 100% w/w formulation.
The composition of the present invention can be applied by any one of the methods selected from atomization, spreading, dusting, spraying, diffusion, immersion, irrigation, injection, mixing, sprinkling (water immersion), foaming, dressing, coating, blasting, fumigation, smoking, smog and painting.
In an embodiment, the present invention provides a process for the preparation of a ME formulation which comprises mixing of solvent, emulsifier, safener, Pinoxaden, Carfentrazone-ethyl, one of Fenoxaprop-p-ethyl or Isoproturon.
In another embodiment, the present invention provides a process for the preparation of a WP formulation which comprises a) mixing of dispersing agent, wetting agent, Pinoxaden, Carfentrazone-ethyl, one of Fenoxaprop-p-ethyl or Isoproturon, defoamer and filler, b) milling in a suitable air jet mill and c) mixing homogeneously in a blender to obtain the formulation.
In another embodiment, the composition of the present invention is effective in the management of post-emergence of monocotyledonous and dicotyledonous weeds. In an embodiment of the present invention, the composition used for the post-emergence control of variety of crops, including but not limited to, in cereals namely wheat, maize, sorghum, rice, barley, oats, triticale etc., soybeans, peanuts, cotton, onions, garlic, asparagus, sugarcane, ornamentals, rubber, as well as protecting crops from herbicidal injury caused by any of the individual components.
The rate of application amount varies depending on, for example, the blending ratio of active ingredients, meteorological condition, dosage form, application time, application method, application place, weed to be controlled, and target crop, in ordinary cases.
The synergistic composition of the present invention provides a number of other advantages:
The embodiments of the present invention are more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations within the scope of the present invention will be apparent to those of skill in the art. Unless otherwise noted, all parts, percentages and ratios reported in the following examples are on a weight basis and all excipients used in the examples were obtained or are available from the chemical suppliers.
The synergistic herbicidal composition of the present invention comprising Pinoxaden, Carfentrazone-ethyl and one of Fenoxaprop-p-ethyl or Isoproturon in ME and WP form is provided in example 1 to 10. The unit of each component of the composition are expressed in “% w/w” i.e. the percentage by weight, relative to the weight of the total solution or composition.
Table 2 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in ME form. In table 2, active ingredients Pinoxaden, Carfentrazone-ethyl, Fenoxaprop-p-ethyl are in technical grade with 98%, 95% and 97% purity respectively. Particularly example 3 and 4 corresponds to column A and B in table 2.
The ingredients were weighed and taken as per table 2. Solvent C9 and n-butanol were taken. Then, castor oil ethoxylate and calcium dodecylbenzene sulfonate were added and stirred well using a high shear mixer. To the mixture, Pinoxaden, Carfentrazone-ethyl, Fenoxaprop-p-ethyl and Mefenpyr diethyl were added one by one with stirring till a clear solution was obtained. The solution was then filtered through proper filtration apparatus to obtain the title herbicidal composition in ME form.
Example 6 to 10
Table 4 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in WP form. In table 4, active ingredients pinoxaden, carfentrazone-ethyl, isoproturon are in technical grade with 98%, 95% and 95% purity respectively. Particularly example 8 corresponds to column C in table 4.
The ingredients were weighed and taken as per table 4. Sodium salt of naphthalene sulfonate condensate/sodium polycarboxylate, sodium alkyl naphthalene sulfonate blend/sodium dioctylsulfosuccinate, dimethyl polysiloxane, china clay were taken. Then, Pinoxaden, Carfentrazone-ethyl and Isoproturon were added and mixed well using proper ribbon blender type mixer.
The mixture was milled using air jet mill by keeping the suitable air pressure. Then, grinding was carried out until a mean particle size of below 10 microns was obtained. After grinding, mixture was mixed homogeneously in a blender to obtain the title herbicidal composition in WP form.
Two experimental trials to evaluate the herbicidal composition of the present invention were conducted at different trial sites in Karnal (Haryana) and Jalandhar (Punjab) against grassy and broad leaved weeds of wheat crop (variety WH 1105 in Karnal and PBW 803 in Jalandhar), which are prevalent in all wheat growing seasons with solo formulations, binary formulations and ternary formulations of the present invention as per the details provided in Table 5 to 13.
The experiment was laid out in Randomized Block Design (RBD). The plot size was 10 m×10 m and the spacing was 20 cm×10 cm. All the recommended agronomic practices were followed throughout the cropping period. The different formulations were weighed according to the doses and diluted in water and applied using high volume knapsack sprayer fitted with a pressure regulator and a vertical bar with one flat fan nozzle at 31/30 days after sowing (DAS) at the locations and evaluated for % WCE (weed control efficiency) at 15, 30, 45 and 60 days after herbicide application (DAHA). 400 L/ha of water was used to dilute recommended doses of the formulation in all trials.
Weeds were collected from one square meter of each experimental plot and were cleaned and separated species wise. Weeds in different species were oven dried and then weight was taken separately. Weed control efficiency for individual species was calculated using the below formula:
Plants from each experimental plot were harvested and grains were separated and weight of grains was taken. Thereafter weight was converted to yield into kg per hectare.
A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. Synergism was calculated by using Colby's method, Weeds, vol. 15 No. 1(January 1967), pp. 20-2.
The synergistic action expected for a given combination of three active components can be calculated as follows:
Where:
Phalaris
Avena
minor
ludoviciana
Chenopodium
Melilotus
album
Medicago
Anagalis
deniculate
arvensis
Rumex sp.
It is evident from the above tables that the herbicidal composition of the present invention gave good control of weeds and higher yield as compared to the reference products (solo or binary composition). Further, the composition of present invention is synergistic.
For phytotoxicity evaluation on wheat crop, following observations were made by observing temporary or long lasting damage to the leaves if any viz., leaf injury on tips and leaf surface, wilting, vein clearing, necrosis, epinasty and hyponasty at 15, 30, 45, 60 DAHA.
From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitations with respect to the specific embodiments illustrated is intended or should be inferred. It should be understood that all such modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111008240 | Feb 2021 | IN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IN2022/050167 | 2/25/2022 | WO |
