DESC:FORM 2

THE PATENTS ACT 1970
(SECTION 39 OF 1970)

&

THE PATENT RULES, 2003

COMPLETE SPECIFICATION
(Section 10 and Rule 13)

HERBICIDAL COMPOSITION OF METSULFURON METHYL, CARFENTRAZONE ETHYL AND PINOXADEN

We, COROMANDEL INTERNATIONAL LIMITED,
an Indian company incorporated under the Companies Act, 1956, and validly existing under the Companies Act, 2013. Having its registered office at Coromandel House, Sardar Patel Road,
Secunderabad – 500 003, Telangana, India

The following specification particularly describes the invention and the manner in which it is to be performed.
FIELD OF THE INVENTION
The present invention relates to a synergistic herbicidal composition comprising of metsulfuron methyl, carfentrazone ethyl and pinoxaden. Particularly the present invention relates to a method for controlling undesired plants or inhibiting their growth, which comprises applying a herbicidally effective amount of the said composition to the undesired plants or to a place where they grow.

BACKGROUND OF THE INVENTION
Weed Management is one of the most important crop intervention practices to counter crop loss. Different physical, mechanical, biological, and chemical methods are employed for the successful management of weeds. Among these chemical weed management practices focus on managing weeds using several chemical formulations which are commonly known as herbicides. Herbicides control the weed species through interference, mitigation, and disruption of the biochemical and physical processes of a cell. When herbicides are applied to a plant, it gets absorbed through plant surfaces and gets translocated to the specific site of action where it produces toxicity in the physiological and biochemical processes and ultimately check the growth and development of plant species.

Herbicides, or chemical weed killers, have largely replaced mechanical methods of weed control in countries where intensive and highly mechanized agriculture is practiced. They provide a more effective and economical means of weed control than cultivation, hoeing, and hand pulling. Together with fertilizers, other pesticides, and improved plant varieties, they have made an important contribution to the increased yields we now have and serve to combat rising costs and shortages of agricultural labor.

At present, many herbicidal compositions have been developed and used, but there are a variety of types of undesired plants represented by weeds to be controlled. Further, undesired plants having lowered sensitivity to herbicides (herbicide-resistant weeds) emerged, and in some applications, practically, herbicides have only insufficient effects. Hence, there is always a need for new active ingredients or new combinations of existing active ingredients to overcome the existing problems faced in the agricultural industry.

Compositions comprising a single herbicidally active component suffer from numerous drawbacks such as formation of resistant weeds, requirement of high amount and concentration of the active ingredient, environmental damage, seepage of the active component into ground water, phytotoxicity and harmful effects on the health of animals and humans.

Active compounds having different mechanisms of action are combined to delay the generation of resistance and reduce the amount of application and prevention and treatment costs. Consequently, research is being conducted to produce herbicides and combinations of herbicides that are safer, that have better performance, that require lower dosages, that are easier to use, and that cost less.

The synergistic herbicidal composition of the present invention can control a wide range of undesired plants emerging in agricultural fields or non-agricultural fields. It has a remarkable herbicidal activity when a composition comprising metsulfuron methyl, Carfentrazone ethyl and pinoxaden, are used in combination.

Metsulfuron-methyl is an organic compound classified as a sulfonylurea herbicide, which kills broadleaf weeds and some annual grasses. It is a pre-emergence and post-emergence herbicide used to control annual grasses, brushes, woody plants, and broadleaf weeds. It can be applied to cereals including barley, rye, and wheat and to pastures. It is primarily used to control brush, woody plants and broadleaf weeds on rights-of-way, fence rows, storage areas, highways, and other non-crop areas.

Metsulfuron methyl is chemically known as methyl 2-(N-((4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)carbamoyl)sulfamoyl)benzoate that inhibits the acetolactate synthase (ALS) in plants as described in US 4,394,506 and has the following structure:

Pinoxaden is a representative of the new phenyl pyrazoline class of chemicals, which is a highly selective systemic herbicide used to control monocotyledonous grass weeds in crops such as wild oats, rye grass and black grass in winter and spring wheat and winter and spring barley. Pinoxaden is developed by Syngenta and is used against grasses. The effect is based on influencing the lipid metabolism of the cells. It inhibits acetyl-CoA carboxylase.

Pinoxaden is approved for post emergence control of grass weeds in wheat (including durum) and barley. One application per crop season by agricultural workers using either open-cab ground boom equipment or via aerial application.

Pinoxaden is chemically known as 8-(2,6-Diethyl-p-tolyl)-1,2,4,5-tetrahydro-7-oxo-7H-pyrazolo[1,2-d][1,4,5]oxadiazepine-9-yl-2,2-dimethylpropionate and is described in US6410480. It has the following chemical structure:

Carfentrazone ethyl is a contact herbicide used to control broadleaf and sedge weeds in cereals. It is applied as a foliar spray and is absorbed through the leaves. Translocation after absorption is limited. It’s mode of action is the disruption of membranes by inhibiting the action of protoporphyrinogen oxidase, causing cell death. It is non-selective, and can be used for complete vegetation control, as well as a desiccant and a defoliant in some crops. Some of the broad-leaved weeds, controlled post-emergence, by Carfentrazone ethyl-ethyl include Galium aparine, Abutilon theophrasti, Ipomoea ederacea var. hederacea, Chenopodium album and several mustard species.

Carfentrazone ethyl is chemically known as Ethyl 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl]-4-fluorophenyl] propionate and is described in US5125958. It has the following chemical structure:

The inventors of the present invention have surprisingly found that formulation of the three active components metsulfuron methyl, carfentrazone ethyl and pinoxaden, has its own benefits such as it has lower application rate that not only reduces the amount of an active substance required for application, but as a rule, also reduces the amount of formulation auxiliaries required. Both reduce the economic outlay and improve the eco-friendliness of the herbicide treatment.

OBJECT OF THE INVENTION

One object of the present invention is to provide a synergistic herbicidal composition comprising metsulfuron methyl, carfentrazone ethyl and pinoxaden.

Another object of the present invention is to provide a synergistic herbicidal composition comprising metsulfuron methyl, carfentrazone ethyl and pinoxaden and other agrochemical additives in effective amounts.

Yet another object of the present invention is to provide a method for controlling undesired plants or inhibiting their growth, which comprises applying a herbicidally effective amount of the said composition to the undesired plants or to a place where they grow.

SUMMARY OF THE INVENTION
The present invention provides a novel herbicidal composition.

One aspect of the present invention is to provide a synergistic herbicidal composition comprising metsulfuron methyl, carfentrazone ethyl and pinoxaden.

Another aspect of the present invention provides a synergistic herbicidal composition comprising of:
a) metsulfuron methyl in a range from 0.2% (w/w) to 2% (w/w),
b) carfentrazone ethyl in a range from 3% (w/w) to 9% (w/w),
c) pinoxaden present in a range from 5% (w/w) to 15% (w/w), and
d) agrochemical additives.

Another aspect of the present invention provides a water dispersible granules (WDG) composition comprising of:
a) metsulfuron methyl in a range from 0.2% (w/w) to 2% (w/w),
b) carfentrazone ethyl in a range from 3% (w/w) to 9% (w/w),
c) pinoxaden present in a range from 5% (w/w) to 15% (w/w), and
d) agrochemical additives.

In an aspect of the present invention, the suitable agrochemical additives are selected from a wetting agent, a dispersing agent, a defoamer, anti-caking agent, co-filler, and filler.

In an aspect of the present invention, the wetting agent is selected from the group comprising of sodium isopropyl naphthalene sulfonate, alkyl naphthalene sulfonate, Propol 990N, and sodium methyl cocoyl taurate, present in a range from 1% to 5% (w/w).

In an aspect of the present invention, the dispersing agent is selected from the group comprising of sodium salt of naphthalene sulfonate condensate, condensed methyl naphthalene sulfonate, blend of dispersing agents (JEEMOL DW18), sodium polycarboxylate, sodium lignosulfonate, Alkyl naphthalene sulfonate condensate and combination thereof, present in a range from 1% to 15% (w/w).

In an aspect of the present invention, the defoamer is silicon antifoam emulsion, present in a range from 0.1% to 1.5% (w/w).

In an aspect of the present invention, the anti-caking agent is silicon dioxide, present in an amount of 0.1% to 3% (w/w).

In an aspect of the present invention, the co-filler is ammonium sulphate, present in a range from 10% to 25% (w/w).

In an aspect of the present invention, the filler is aluminum silicate (china clay), present in Q.S.

Yet another aspect of the present invention provides a process for the preparation of a water dispersible granules (WDG) composition comprising of metsulfuron methyl, carfentrazone ethyl and pinoxaden.

Yet another aspect of the present invention provides a synergistic composition comprising of metsulfuron methyl, carfentrazone ethyl and pinoxaden formulation with an improved stability and ready to use herbicidal composition, having superior bio-efficacy compared to the individual formulations.

Yet another aspect of the present invention provides a method for controlling undesired plants or inhibiting their growth, which comprises applying a herbicidally effective amount of the said composition to the undesired plants or to a place where they grow.

The present invention relates to herbicidal composition with synergistic activity. The composition contains three active ingredients that mutually complement each other when used together and exhibit activity that is greater than the activities of individual components when used alone.

The present invention discloses a co-formulation of metsulfuron methyl, carfentrazone ethyl and pinoxaden, which results in synergistic mixture that is more effective than the individual compounds at the considered doses. The composition of the present invention decreases application rates of each of the active ingredients and is non-phytotoxic. Thus, it is effective to reduce the environmental load on an area where the composition is applied or a surrounding area thereof.

DESCRIPTION OF THE INVENTION
The term "comprising", which is synonymous with "including", "containing", or "characterized by” here is defined as being inclusive or open-ended, and does not exclude additional, unrecited elements or method steps, unless the context clearly requires otherwise.

It is to be noted that, as used in the specification, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.

As used herein, the terms "crops" and "vegetation" can include, for instance, dormant seeds, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation.

As used herein, immature vegetation may be understood to include small vegetative plants prior to reproductive stage, and mature vegetation may be understood to include vegetative plants during and after the reproductive stage.

As used herein, the terms “herbicide” may be understood as a substance that is toxic to plants, used to destroy unwanted vegetation.

As used herein, the term “synergistic composition” may be understood to include effective combination of more than one agrochemical that allows the application of the said agrochemical in a much lower dosage, which results in a less dosage treatment for the crops.

As used herein, the term “agrochemical additives” may be understood to include a range of surfactants, dispersing agents, organic or inorganic pigments, solvents, de-solvents, defoamers, and emulsions, crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, neutralizers or pH adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, lubricants, thickeners, anti-freezing agents, sterilization agents among others.

The herbicidal composition of the present invention may be 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 or WDG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW) among others. Preferably, the composition of the present invention is formulated as water dispersible granules (WDG).

One embodiment of the present invention is to provide a synergistic herbicidal composition comprising metsulfuron methyl, carfentrazone ethyl and pinoxaden.

Another embodiment of the present invention provides a synergistic herbicidal composition comprising of:
a) metsulfuron methyl in a range from 0.2% (w/w) to 2% (w/w),
b) carfentrazone ethyl in a range from 3% (w/w) to 9% (w/w),
c) pinoxaden present in a range from 5% (w/w) to 15% (w/w), and
d) agrochemical additives.

Another embodiment of the present invention provides a water dispersible granules (WDG) composition comprising of:
a) metsulfuron methyl in a range from 0.2% (w/w) to 2% (w/w),
b) carfentrazone ethyl in a range from 3% (w/w) to 9% (w/w),
c) pinoxaden present in a range from 5% (w/w) to 15% (w/w), and
d) agrochemical additives.

According to the present invention, the suitable agrochemical additives are selected from a wetting agent, a dispersing agent, a defoamer, anti-caking agent, co-filler, and a filler.

According to the present invention, the wetting agent is selected from the group comprising of sodium isopropyl naphthalene sulfonate, alkyl naphthalene sulfonate, Propol 990N, and sodium methyl cocoyl taurate, present in a range from 1% to 5% (w/w).
According to the present invention, the dispersing agent is selected from the group comprising of sodium salt of naphthalene sulfonate condensate, condensed methyl naphthalene sulfonate, blend of dispersing agents (JEEMOL DW18), sodium polycarboxylate, sodium lignosulfonate, Alkyl naphthalene sulfonate condensate and combination thereof, present in a range from 1% to 15% (w/w).

According to the present invention, the defoamer is silicon antifoam emulsion, present in a range from 0.1% to 1.5% (w/w).

According to the present invention, the anti-caking agent is silicon dioxide, present in an amount of 0.1% to 3% (w/w).

According to the present invention, the co-filler is ammonium sulphate, present in a range from 10% to 25% (w/w).

According to the present invention, the filler is aluminum silicate (china clay), present in Q.S.

Yet another embodiment of the present invention provides a process for the preparation of a water dispersible granules (WDG) composition comprising of metsulfuron methyl, carfentrazone ethyl and pinoxaden.

The composition of the present invention and method provided may be utilized to control weeds or battle undesired vegetation in crops or other settings, including but not limited to cereals, such as wheat, barley, rye, oats, corn/maize, rice, sorghum, triticale and related crops; fruit, such as pomes, stone fruit and soft fruit, for example apples, grapes, pears, plums, peaches, almonds, cherries, and berries, for example strawberries, raspberries and blackberries; leguminous plants, for examples beans, lentils, peas, soybeans, peanut; oil plants, for example rape, mustard, and sunflower; cucurbitaceae, for example marrows, cucumbers, melons; fibre plants, for example cotton, flax, hemp, jute; citrus fruit, for example oranges, lemons, grapefruit and mandarins; vegetable, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paparika; as well as ornamentals, such as flowers, shrubs, broad-leaved trees and evergreens, for example conifers, pastures, grasslands, rangelands, fallow and, turf, tree and vine orchards, and industrial vegetation management. Preferably, the undesirable vegetation includes species from the families of broadleaved and grass weeds, more preferably from the families of Aeschynomene, Ageratum, Amaranthus, Bidens, Brachiaria, Cenchrus, Cyperus, Digitaria, Echinochloa, Eclipta, Eleusine, Eragrostis Fimbristylis, Galinsoga, Ischaemum, Leptochloa, Monochoria, Panicum, Paspalum, Polygonum, Portulaca, Richardia, Sesbania, Setaria, Sida, Sorghum, most preferably Echinochloa, Leptochloa, Ischaemum, Monochoria, and Cyperus, or combinations thereof. It has been surprisingly found that the herbicidal composition of the present invention delays the appearance of the resistant strains of weeds and achieves effective and economical control of undesired weeds.

The composition achieves improved biological activity by enhancing overall control of weeds over a shorter period. Additional benefits of using the herbicidal composition of the present invention includes reduced risk of occupational hazard, lower cost of application, better cost: benefit ratio to the end user, reduced fuel, and labor cost, saving in applicator’s time and loss caused by mechanical damage to the crop and soil.

The present compositions can be applied to the undesirable vegetation and/or weeds or their locus using conventional ground or aerial dusters, sprayers, and granule applicators, by addition to irrigation or paddy water, and by other conventional means known to those skilled in the art.

The present invention is further illustrated by the following examples which are provided merely to be exemplary of the inventions and is not intended to limit the scope of the invention. Certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the present invention.
Examples:
Example-1: The illustrative embodiments show the composition of Metsulfuron methyl + Carfentrazone-ethyl + Pinoxaden in water dispersible granules (WDG) form in different amount as follows:

Table-1: Metsulfuron-methyl 1% + Carfentrazone ethyl 5% + Pinoxaden 10% WDG
S. No Compositions Function Charge in (%)
1. Metsulfuron methyl Active ingredient 1.0
2. Carfentrazone ethyl Active ingredient 5.0
3. Pinoxaden Active ingredient 10.0
4. Alkyl naphthalene sulfonate Wetting agent 5.0
5. Sodium salt of naphthalene sulfonate condensate Dispersing agent 2.0
6. Silicone antifoam emulsion Defoamer 0.5
7. Silicon dioxide Anti caking agent 1.0
8. Ammonium sulphate Co-filler 15.0
9. Aluminium silicate
(china clay) Filler Q.S.

Process for manufacture of composition is as follows:
Step 1: Weighing all the following raw materials according to the batch size in a pre-blender and mixing it for 1 hour.
• filler,
• co-filler,
• anticaking agent,
• wetting agent,
• dispersing agent,
• defoamer,
• metsulfuron methyl,
• carfentrazone ethyl, and
• pinoxaden,
Step 2: Pre-mix the sample in a blender.
Step 3: Mill the sample, through Air Jet mill instrument.
Step 4: Collect the Air Jet milled sample and post blend in a blender.
Step 5: Prepare a mixture of water and defoamer for dough preparation.
Step 6: Extrude the granules through Basket extruder.
Step 7: Collect the WDG and dry in fluid bed dryer (FBD) @ 50°C, check the moisture content it should be < 5.0%.
Note: While drying the WDG in FBD, air flow rate should be maintained between 50-60.
Step 8: Submit the sample for Analysis.
Step 9: Pack the material appropriately (TLP bag).

Table-2: Metsulfuron methyl 0.2% + Carfentrazone ethyl 3% + Pinoxaden 5% WDG
S. No Compositions Function Charge in (%)
1. Metsulfuron-methyl Active ingredient 0.2
2. Carfentrazone ethyl Active ingredient 3.0
3. Pinoxaden Active ingredient 5.0
4. Alkyl naphthalene sulfonate Wetting agent 5.0
5. Condensed methyl naphthalene sulfonate Dispersing agent 10.0
6. Ammonium sulphate Co-filler 15.0
7. Silicone antifoam emulsion Defoamer 1.5
8. Silicon dioxide Anti caking agent 1.0
9. Aluminium silicate
(china clay) Filler Q.S.

The process for manufacture of composition is similar to the procedure as described in Table-1.
Table-3: Metsulfuron methyl 1.5% + Carfentrazone ethyl 7% + Pinoxaden 10% WDG
S. No Compositions Function Charge in (%)
1. Metsulfuron-methyl Active ingredient 1.5
2. Carfentrazone ethyl Active ingredient 7.0
3. Pinoxaden Active ingredient 10.0
4. Sodium Polycarboxylate Dispersing agent 5.0
5. Blend of dispersing agents (JEEMOL DW18) Dispersing agent 5.0
6. Ammonium sulphate Co-filler 20.0
7. Silicone antifoam emulsion Defoamer 1.5
8. Silicon dioxide Anti caking agent 0.1
9. Aluminium silicate
(china clay) Filler Q.S.

The process for manufacture of composition is similar to the procedure as described in Table-1.

Table-4: Metsulfuron methyl 1.5% + Carfentrazone ethyl 8% + Pinoxaden 15% WDG
S. No Compositions Function Charge in (%)
1. Metsulfuron-methyl Active ingredient 1.5
2. Carfentrazone ethyl Active ingredient 8.0
3. Pinoxaden Active ingredient 15.0
4. Propol 990 N Wetting agent 2.5
5. Sodium lignosulfonate Dispersing agent 10.0
6. Ammonium sulphate Co-filler 10.0
7. Silicone antifoam emulsion Defoamer 1.0
8. Silicon dioxide Anti caking agent 3.0
9. Aluminium silicate
(china clay) Filler Q.S.

The process for manufacture of composition is similar to the procedure as described in Table-1.

Table-5: Metsulfuron methyl 2% + Carfentrazone ethyl 9% + Pinoxaden 5% WDG
S. No Compositions Function Charge in (%)
1. Metsulfuron-methyl Active ingredient 2.0
2. Carfentrazone ethyl Active ingredient 9.0
3. Pinoxaden Active ingredient 5.0
4. Sodium methyl cocoyl taurate Wetting agent 5.0
5. Alkyl naphthalene sulfonate condensate Dispersing agent 12.0
6. Ammonium sulphate Co-filler 25.0
7. Silicone antifoam emulsion Defoamer 1.5
8. Silicon dioxide Anti caking agent 0.1
9. Aluminium silicate
(china clay) Filler Q.S.

The process for manufacture of composition is similar to the procedure as described in Table-1.

Example 2: Efficacy study of Metsulfuron-methyl 1% + Carfentrazone ethyl 5% + Pinoxaden 10% in water dispersible granules (WDG) form:

SYNERGY STUDIES:
Wheat is the main cereal crop in India. In India, it is grown on an area of 31.6 million hectare with an annual production of 106.84 million tons. Successful weed control is the most important factor for fruitful wheat production because losses due to weeds have been one of the major limiting factors in wheat production. Weeds compete with crops for light moisture and nutrients. It was concluded that weeds exhibit economic yield losses to the wheat crop, which may range from 24-39.95% and these must be controlled during the full growing season of the crop for achieving satisfactory crop yields. Traditionally, weed control in India has been largely dependent on manual weeding. However, increased labour scarcity and costs are encouraging farmers to adopt to use herbicides.

The field studies were conducted to compare the weed controlling activity of the combination of Metsulfuron methyl, Carfentrazone ethyl and Pinoxaden. The active ingredient Pinoxaden in the combination, belongs to the chemical class of phenyl pyrazolines and its mode of action is based on inhibition of the Acetyl-coenzyme A carboxylase. Metsulfuron Methyl are belonging to chemical class Sulfonylureas with ALS inhibitor (inhibition of acetolactate synthase) mode of action & Carfentrazone ethyl belongs to Chemical class N-Phenyl-triazolinones and its mode of action is based on protoporphyrinogen oxidase. Combination has the potential of controlling the cross-spectrum weeds (broad leaf weeds & grassy weeds) in wheat at the post-emergence (30-40 DAS or 10 days after 1st irrigation to wheat) application timing. All the molecules are safe to wheat when applied at their recommended dose rate in post-emergence (30-40 DAS or 10 days after 1st irrigation to wheat) application timing.

The weed control activity of the individual herbicides of the invention and their combinations were evaluated on weeds such as Phalaris minor, Melilotus alba, Rumex dentatus & Chenopodium album. Trials were conducted with randomized block design with net plot size of 5 m x 6 m. Each trial was replicated four times and conducted under GEP guidelines. Spraying was done with manual operated backpack knapsack sprayer with 400 L of water spray volume per hectare at post-emergence application timing. Such field trials were carried out at various locations to generate independent data, the locations were chosen randomly across India.

Visual observations were recorded on percent weed control for individual weeds on whole plot basis at 30 days after application. These observations are to be taken from the entire plot.
Appropriate analysis of plant response to herbicide combination is critical in determining the type of activity observed. The most widely used model is the one Gowing* derived and Colby** modified. Gowing described a mathematical formula for calculating the predicting response values for pesticide mixtures. He suggested the expected (E) percent inhibition of growth induced by pesticide A plus pesticide B and plus pesticide C is as follows, *(Jerry Flint et al, 1988) ***

(AB + AC + BC) ABC
Expected (E) = A + B + C - +
100 10000
Where,
A = observed efficacy of active ingredient A at the same concentration as used in the mixture.
B = observed efficacy of active ingredient B at the same concentration as used in the mixture.
C = observed efficacy of active ingredient C at the same concentration as used in the mixture.

When the percentage of pesticidal control observed for the combination is greater than the expected percentage, there is a synergistic effect. (Ratio of O/E > 1, means synergism observed)

Reference:
*Gowing, D. P. 1960. Comments on tests of herbicide mixtures. Weeds 8:379–391.
**Colby, S. R. 1967. Calculating synergistic and antagonistic responses of herbicide combinations. Weeds 15:20–22
*** Jerry Flint et al, 1988. Analyzing Herbicide Interactions: A Statistical Treatment of Colby's Method. Weed Technology 2: 304-309

The herbicide combinations, application rates, plant species tested, and results are given in the following tables:
Table 6: Demonstrates synergy on weeds using the combination of Metsulfuron methyl, Carfentrazone ethyl and Pinoxaden in post-emergence application window. The field trials were carried out in India at various locations. The percentage efficacy was calculated after 30 days of application. The target weed was Phalaris minor, and the results are recorded in the below table.
Active Dose (GAH) % Weed Control of Phalaris minor
Expected Observed
Pinoxaden 5.1% EC 40 75
Metsulfuron methyl 20% WP 4 15
Carfentrazone ethyl 40% DF 20 15
Pinoxaden 5.1% EC + Metsulfuron methyl 20% WP 40 + 4 78.75 75
Ratio of O/E 0.95
Metsulfuron methyl 20% WP + Carfentrazone ethyl 40% DF 4 + 20 27.75 20
Ratio of O/E 0.72
Carfentrazone ethyl 40% DF + Pinoxaden 5.1% EC 20 + 4 78.75 75
Ratio of O/E 0.95
Metsulfuron methyl 1% + Carfentrazone ethyl 5% +
Pinoxaden 10% WDG 64 81.93 85
Ratio of O/E 1.03
EC – Emulsion concentrate; WP – Wettable powder; DF – Dry flowable; WDG – Water dispersible granules; and GAH – Gram Active per hectare.

The results in table 6, clearly demonstrate synergy between three-way combination of Metsulfuron methyl, Carfentrazone ethyl and Pinoxaden in post-emergence application timing against Phalaris minor. The higher ratio of the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination. However, all two-way combinations showed lower ratio of the observed and the expected efficacy, which clearly showed the no synergistic effect of the combination against weeds like Phalaris minor.

Table 7: Demonstrates synergy on weeds using the combination of Metsulfuron methyl, Carfentrazone ethyl and Pinoxaden in post-emergence application window. The field trials were carried out in India at various locations. The percentage efficacy was calculated after 30 days of application. The target weed was Malva parviflora, Melilotus alba & Rumex dentatus and the results are recorded in the below table.
Active Dose (GAH) % Weed Control of Malva parviflora % Weed Control of Melilotus alba % Weed Control of Rumex dentatus
Expected Observed Expected Observed Expected Observed
Pinoxaden 5.1% EC 40 10 5 5
Metsulfuron methyl 20% WP 4 40 85 70
Carfentrazone ethyl 40% DF 20 80 82 85
Pinoxaden 5.1% EC + Metsulfuron methyl 20% WP 40 + 4 46 40 85.75 85 71.5 70
Ratio of O/E 0.86 0.99 0.97
Metsulfuron methyl 20% WP + Carfentrazone ethyl 40% DF 4 + 20 88 80 97.3 97 95.5 95
Ratio of O/E 0.98 0.99 0.99
Carfentrazone ethyl 40% DF + Pinoxaden 5.1% EC 20 + 4 82 80 82.9 82 85.75 85
Ratio of O/E 0.98 0.99
Metsulfuron-methyl 1% + Carfentrazone ethyl 5% + Pinoxaden 10% WDG 64 89.2 95 97.4 100 95.72 100
Ratio of O/E 1.01 1.02 1.04
EC – Emulsion concentrate; WP – Wettable powder; DF – Dry flowable; WDG – Water dispersible granules; and GAH – Gram Active per hectare.

The results in table 7, clearly demonstrate synergy between three-way combination of Metsulfuron methyl, Carfentrazone ethyl and Pinoxaden in post-emergence application timing against Malva parviflora, Melilotus alba & Rumex dentatus. The higher ratio of the observed and the expected efficacy clearly demonstrates the synergistic effect of the combination. However, all 2-way combinations showed lower ratio of the observed and the expected efficacy, which clearly showed the no synergistic effect of the combination against weeds like, Malva parviflora, Melilotus alba & Rumex dentatus
,CLAIMS:WE CLAIM:
1. A synergistic herbicidal composition comprising of metsulfuron methyl, carfentrazone ethyl, and pinoxaden.

2. The composition as claimed in claim 1, wherein the composition is formulated as water dispersible granules (WDG) form.

3. The composition as claimed in claim 1, wherein the composition comprising of:
a) metsulfuron methyl in a range from 0.2% (w/w) to 2% (w/w),
b) carfentrazone ethyl in a range from 3% (w/w) to 9% (w/w),
c) pinoxaden present in a range from 5% (w/w) to 15% (w/w), and
d) agrochemical additives.

4. The composition as claimed in claim 3, wherein the agrochemical additives are selected from a wetting agent, a dispersing agent, a defoamer, an anti-caking agent, a co-filler, and a filler.

5. The composition as claimed in claim 4, wherein the wetting agent is selected from sodium isopropyl naphthalene sulfonate, alkyl naphthalene sulfonate, Propol 990N, and sodium methyl cocoyl taurate, present in a range from 1% to 5% (w/w).

6. The composition as claimed in claim 4, wherein the dispersing agent is selected from sodium salt of naphthalene sulfonate condensate, condensed methyl naphthalene sulfonate, blend of dispersing agents (JEEMOL DW18), sodium polycarboxylate, sodium lignosulfonate, Alkyl naphthalene sulfonate condensate and combination thereof, present in a range from 1% to 15% (w/w).

7. The composition as claimed in claim 4, wherein the defoamer is silicone antifoam emulsion, present in a range from 0.1% to 1.5% (w/w).

8. The composition as claimed in claim 4, wherein the anti-caking agent is silicon dioxide, present in an amount of 0.1% to 3% (w/w).

9. The composition as claimed in claim 4, wherein the co-filler is ammonium sulphate, present in a range from 10% to 25% (w/w).

10. The composition as claimed in claim 4, wherein the filler is aluminum silicate (china clay), present in Q.S

Dated this Twentieth (20th) day of November, 2023

_____________________________
Dr. S. Padmaja
Agent for the Applicant
IN/PA/883