The present invention relates to an herbicidal composition comprising of cyclohexanedione class of herbicidal compounds such as clethodim, aryloxyphenoxy propionate class of herbicidal compounds such as fenoxaprop-p-ethyl and at least one herbicidal compound selected from oxyfluorfen or fomesafen and agriculturally acceptable additives and uses thereof and process of preparing the herbicidal composition.
BACKGROUND OF THE INVENTION
Weeds and other unwanted vegetation inhibiting 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 in combination of active ingredients for the control of such weeds or unwanted plants. Formulation of chemical herbicides of many types have been disclosed in the literature and a large number of them are in commercial use.
Indian patent application No. 201637034511 discloses a herbicidal composition comprising a first compound belonging to the aryloxyphenoxypropionate family selected from quizalofop-p-ethyl, haloxyfop, propaquizafop, quizalofop-p-tefuryl, fluazifop-p-butyl, fenoxaprop-p-ethyl, the isomers of these compounds and the salts of these compounds; and a second compound belonging to the family cyclohexanediones selected from the group consisting of clethodim, cycloxydim, tepraloxydim, isomers of these compounds and salts thereof. However, the patent application fails to teach a composition comprising three active ingredients.
Currently, in order to reduce the risk from increased number of herbicide resistant varieties of weeds, combinations 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 successful control of weeds over a relatively longer period of time and preventing development of resistance. However, this requires

continuous development of effective compositions with different active ingredients, so as to avoid selection to the particular mechanism of action.
Therefore, there exists a need to develop an herbicidal composition which is compatible and 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 control the development of resistant varieties to the active ingredients or to the mixtures of known active ingredients used by farmer while minimising the doses of chemical products sprayed in the agricultural fields.
As a solution to the above mentioned problems, the inventors of the present invention surprisingly found that composition comprising clethodim, fenoxaprop-p-ethyl and at least one herbicidal compound selected from oxyfluorfen or fomesafen provides effective control of wide range of weeds or undesired plants.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a combination comprising of clethodim, fenoxaprop-p-ethyl and at least one herbicidal compound selected from oxyfluorfen or fomesafen.
In one aspect, the present invention provides a composition comprising of clethodim, fenoxaprop-p-ethyl and at least one herbicidal compound selected from oxyfluorfen or fomesafen with at least one agriculturally acceptable additive.
In another aspect, the present invention provides a composition comprising of clethodim, fenoxaprop-p-ethyl, oxyfluorfen and at least one agriculturally acceptable additive.
In another aspect, the present invention provides a composition comprising of clethodim, fenoxaprop-p-ethyl, fomesafen and at least one agriculturally acceptable additive.
In another aspect, the composition according to the present invention comprises clethodim in an amount in the range from 10-20% w/w, fenoxaprop-p-ethyl in an amount in the range from 5-15% w/w, and oxyfluorfen in an amount in the range from 5-25% w/w.

In another aspect, the composition according to the present invention comprises clethodim in an amount in the range from 10-13% w/w, fenoxaprop-p-ethyl in an amount in the range from 5-20% w/w, and fomesafen in an amount in the range from 10-20%) w/w.
In an aspect, the composition of the present invention is formulated as Emulsifiable Concentrate (EC).
In another aspect, the composition of the present invention comprises one or more agriculturally acceptable additive selected from the group comprising of solvent(s), emulsifier(s), safener(s) or a combination thereof and other additives, if required in a formulation.
DETAILED DESCRIPTION OF THE INVENTION
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.
It is to be noted that, as used in the specification and the appended claims, 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 "comprises", "comprising", "includes", "including", or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition or a method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, or method.

As used herein, the terms "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 clethodim, fenoxaprop-p-ethyl and at least one herbicidal compound selected from oxyfluorfen or fomesafen thereof.
As used herein, the term "agriculturally acceptable additive (s)" refers to inert substances and are auxiliary substances added to the processing or use of pesticide preparations and used to improve the physical and chemical properties of formulations. The auxiliaries themselves are essentially free of biological activity, but can affect the control effect.
As used herein, the term "solvent(s)" refers to liquids chemicals that are added to an herbicidal product to aid in the delivery of the active ingredient.
As used herein, the term "emulsifier(s)" refers to a group of chemicals belonging to the surfactant family and stabilizes emulsions. Emulsifiers blend and hold together ingredients that would not normally mix very well.
As used herein, the term "safener(s)" refers to an agent that reduces or avoids phytotoxic side-effects of an herbicide.
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 "effective amount" means the amount of the active substances in the compositions to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target weeds. An effective amount of the compositions will also vary according to the prevailing conditions such as desired herbicidal effect and duration, weather, target species, locus, mode of application, and the like.
As used herein, the term "herbicide", refers to any chemical substance used to destroy/kill, delay, reduce, inhibit or otherwise adversely affect the growth of plants, especially weeds.

As used herein, the term "clethodim" encompasses its agrochemically acceptable salt(s), derivative(s) or any other modified form of clethodim. Clethodim having IUPAC name (5RS)-2-[(lEZ)-l-[(2E)-3-chloroallyloxyimino]propyl]-5-[(2RS)-2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-l-one, belongs to the group of cyclohexanedione oxime herbicide. It acts by inhibition of acetyl-coenzyme A carboxylase. It is a systemic herbicide, rapidly absorbed and readily translocated from treated foliage to the root system and growing parts of the plant. It is used for post-emergence control of annual and perennial grass weeds in a wide range of broad leaved crops, including soybeans, cotton, flax, sunflowers, alfalfa, peanuts, oilseed rape, sugar beets, tobacco, potatoes, vegetables, trees and vines.
As used herein, the term "fenoxaprop-p-ethyl" encompasses its agrochemically acceptable salt(s), ester(s), derivative(s) or any other modified form of fenoxaprop-p-ethyl. Fenoxaprop-p-ethyl having RJPAC name ethyl (R)-2-[4-(6-chloro-l,3-benzoxazol-2-yloxy)phenoxy] propionate; ethyl (R)-2-[4-(6-chlorobenzoxazol-2-yloxy)phenoxy]propionate, belongs to the group of aryloxyphenoxypropionate herbicide. It acts by inhibition of acetyl CoA carboxylase. It is a selective herbicide with contact and systemic action, absorbed principally by the leaves, with translocation both acropetally and basipetally to the roots or rhizomes. It is used for post-emergence control of annual and perennial grass weeds in potatoes, beans, soybeans, beets, vegetables, peanuts, flax, oilseed rape and cotton.
As used herein, the term "oxyfluorfen" encompasses its agrochemically acceptable salt(s), derivative(s) or any other modified form of oxyfluorfen. Oxyfluorfen having RJPAC name 2-chloro-a, a, a-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether, belongs to the group of diphenyl ether herbicide. It acts by inhibition of protoporphyrinogen oxidase (PPO). It is a selective contact herbicide, absorbed more readily by foliage (and especially the shoots) than by roots with very little translocation. It is used for pre-emergence and post-emergence control of annual broad leaved and grass weeds in tree fruit, citrus, vines, nuts, cereals, maize, soybeans, peanuts, rice, cotton, bananas, peppermint, onions, garlic, ornamentals and conifer seedbeds.
As used herein, the term "fomesafen" encompasses its agrochemically acceptable salt(s), derivative(s) or any other modified form of fomesafen. Fomesafen having IUPAC name 5-(2-chloro- a, a, a-trifluoro-p-tolyloxy)-N-mesyl-2-nitrobenzamide, belongs to the group of diphenyl ether herbicide. It acts by inhibition of protoporphyrinogen oxidase (PPO). It is a selective herbicide, absorbed by both leaves and roots, with very limited translocation in the ohloem. It is used for earlv Dost-emereence control of broad-leaved weeds in sovbeans.

Accordingly, the present invention provides a combination of clethodim, fenoxaprop-p-ethyl and at least one herbicidal compound selected from oxyfluorfen or fomesafen.
In an embodiment, the present invention provides a synergistic herbicidal composition comprising of clethodim, fenoxaprop-p-ethyl and at least one herbicidal compound selected from oxyfluorfen or fomesafen and at least one agriculturally acceptable additives.
It has been surprisingly found that composition comprising of clethodim, fenoxaprop-p-ethyl and at least one herbicidal compound selected from oxyfluorfen or fomesafen not only provides effective control of weeds or undesired plants but also such combination is synergistic in nature.
In an embodiment, the composition according to the present invention comprises clethodim in an amount in the range from 10-20% w/w, fenoxaprop-p-ethyl in an amount in the range from 5-15% w/w, and oxyfluorfen in an amount in the range from 5-25% w/w.
In another embodiment, the composition according to the present invention comprises clethodim in an amount in the range from 10-13%) w/w, fenoxaprop-p-ethyl in an amount in the range from 5-20% w/w, and fomesafen in an amount in the range from 10-20%) w/w.
In yet another embodiment, the composition of the present invention is selected from a group comprising:
• clethodim present in an amount 12% w/w, fenoxaprop-p-ethyl present in an amount 10%) w/w and oxyfluorfen present in an amount 10%> w/w and at least one agriculturally acceptable additives.
• clethodim present in an amount 12% w/w, fenoxaprop-p-ethyl present in an amount 8% w/w and fomesafen present in an amount 12.5% w/w and at least one agriculturally acceptable additives.
In yet another embodiment, the composition of the present invention is formulated as Emulsifiable Concentrate (EC).
The composition of the present invention comprises agriculturally acceptable additives selected from the group comprising of solvent(s), emulsifier(s), safener(s) or a combination thereof and other additives if required in a formulation.

Solvent(s) is selected from the group comprising of, but not limited to alcohols such as ethanol, propanol, butanol, n-octanol, isopropanol, glycol ether based solvent such as 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, cyclohexanone, isophorone; ethers such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, isoparaffin, kerosene, mineral oils; vegetable oils such as epoxidized soybean oil (ESBO/ESO); aromatic hydrocarbons such as solvent naphtha, aromatic heavy naphtha, solvent C9, solvent CIO, 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-methyl-2-pyrrolidone (NMP), N-octylpyrolidone, decanamide, N,N-dimethyldecanamide; nitriles such as acetonitrile; organosulfur compound such as dimethyl sulfoxide. These solvents may be used alone or in combination thereof or as a co-solvent and combination of solvents. The solvent(s) may be used in an amount of quantity sufficient to make 100%w/w formulation.
Emulsifier is selected from the group comprising of, but not limited to, Polyalkylene oxide block copolymer, High molecular weight polymer, PEG-10, PPG-5 cetyl phosphate, nonionic emulsifier such as Tristyryl phenolethoxylate, blend of nonionic-anionic emulsifiers such as castor oil ethoxylates, alkoxylated alcohols, ethoxylated amines, ethoxylated tristyrylphenol, fatty acid ethoxylates, calcium salts of dodecylbenzene sulphonate, salts of phosphate esters of ethoxylated tristyrylphenol. These emulsifiers may be used alone or in combination thereof. The emulsifier is present in an amount in the range from 1 to 20% w/w.
Safener(s) is selected from the group comprising of, but not limited to, benoxacor, cloquintocet mexyl, cyprosulfamide, dichlormid, fenclorim, fenchlorazole, furilazole, isoxadifen, mefenpyr, mefenpyr diethyl, naphthalic acid anhydride, 4-(dichloroacetyl)-l-oxa-4- azaspiro[4.5]decane and 2,2,5-trimethyl-3- (dichloroacetyl)-l,3-oxazolidine. These safeners may be used alone or in combination thereof. The safener is present in an amount in the range from 0.1 to 5% w/w.
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.
The present invention also provides a process of preparing a composition comprising: a) clethodim, fenoxaprop-p-ethyl and at least one herbicidal compound selected from oxyfluorfen or fomesafen; and b) at least one agriculturally acceptable additives.
In another embodiment, the composition of the present invention is effective in the management of post-emergent monocotyledonous and dicotyledonous weeds such as Echinochloa spp., Cyperus spp. Dactyloctenium aegyptium, Cynodon dactylon, Eclipta alba, Commelina spp., Parthenium hysterophorus, Phyllanthus niruri.
In an embodiment of the present invention, the composition used for the post-emergence control of weeds in a variety of crops, including but not limited to, weeds in cotton, oilseeds, fibre crops, sugar crops, peppermint, sugarcane, rubber, oil palms, ornamental trees and bushes, non-crop land, as well as protecting crops from herbicidal injury caused by any of the individual components.
The rate of dosage of formulation varies depending on, for example, the blending ratio of active ingredients, metrological condition, dosage form, application time, application method, application place, weed to be controlled, and a target crop, in ordinary cases.
The synergistic composition of the present invention provides a number of other advantages:
• Increased efficacy in comparison to the other formulations tested during the trial.
• Economically beneficial to the farmers as it provides better yield of the crop with reduction in the number of sprays.
• Reduction in quantity of water required for sprays.
• Reduced possibility of hazards to the farmers due to occupational exposure because of reduction in the number of sprays.
• Is storage stable.
• Is non-phytotoxic.
• Environment friendly.
• Easily applied using drone or by any other aerial means.

• Reduction in generation of empty pesticide containers, thereby, reducing environmental concerns for their disposal.
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 ratio 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.
EXAMPLES
The synergistic herbicidal composition of the present invention comprising clethodim, fenoxaprop-p-ethyl and a) at least one herbicidal compound selected from oxyfluorfen or fomesafen and b) at least one agriculturally acceptable additives to make Emulsifiable Concentrate (EC) formulation is provided in tables 1-4 and examples 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.
Examples 1 to 5
Table 1: Clethodim + Fenoxaprop-p-ethyl + Oxyfluorfen EC

S.N. Ingredients Eg:l Eg: 2 Eg: 3 Eg: 4 Eg: 5

% w/w % w/w % w/w % w/w % w/w
1 Clethodim Technical (100% Basis) 12 20 10 20 10
2 Fenoxaprop-p-ethyl Technical (100% Basis) 10 5 12 10 15
3 Oxyfluorfen Technical (100% Basis) 10 5 25 10 20
4 Safener (Mefenpyr diethyl) 2 1 2 2 3
5 Emulsifier (Blend of non-ionic and anionic) 10 12 14 12 14
6 Solvent 1 (NMP, butanol, isophorone, vegetable oil) 10 10 10 10 10
7 Solvent 2 (aromatic heavy naphtha, C-9, N,N-dimethyl decanamide, cyclohexanone, isophorone etc.) Q.S.to
make
100% Q.S.to
make
100% Q.S.to
make
100% Q.S.to
make
100% Q.S.to
make
100%
Total 100 100 100 100 100

Q.S.: quantity sufficient required to make 100% w/w formulation
Process of preparing synergistic Emulsifiable Concentrate (EC) herbicidal composition comprising Clethodim + Fenoxaprop-p-ethyl + Oxyfluorfen
Table 2 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in Emulsifiable Concentrate form. In table 2, active ingredients Clethodim + Fenoxaprop-p-ethyl + Oxyfluorfen are in technical grade form and their purity considered accordingly to make the formulation. Examples 1-5 of table 1 corresponds to column A-E in table 2.
Table 2: Quantities of active ingredients and raw material charged

s.
N. Ingredients Quantity (g)

A B C D E
1 Clethodim Technical (37% Basis) 32.44 54.06 27.03 54.06 27.03
2 Fenoxaprop-p-ethyl Technical (95% Basis) 10.53 5.27 12.64 10.53 15.79
3 Oxyfluorfen Technical (97% Basis) 10.31 5.16 25.78 10.31 20.62
4 Mefenpyr diethyl 02.10 1.05 2.10 2.10 3.15
5 Emulsifier (Blend of non-ionic and anionic) 10.00 12.00 14.00 12.00 14.00
6 Solvent 1 (isophorone) 15.00 10.00 10.00 10.00 10.00
7 Solvent 2 (aromatic heavy naphtha) 19.62 12.46 8.45 1.00 9.41
Total 100.00 100.00 100.00 100.00 100.00
The ingredients were weighed and taken as per table 2. In a container, solvent and co-solvent were taken and Clethodim, Fenoxaprop-p-ethyl, Oxyfluorfen and Mefenpyr diethyl were added under stirring. Emulsifier was added under stirring. The mixture was stirred to obtain a homogeneous solution. The homogenous solution was filtered to obtain title herbicidal composition.
Example 6 to 10
Table 3: Clethodim +Fenoxaprop-p-ethyl +Fomesafen EC

S.N. Ingredients Eg: 6 Eg: 7 Eg: 8 Eg: 9 Eg: 10

% w/w % w/w % w/w % w/w % w/w

1 Clethodim Technical (100% Basis) 12 10 12 11 13
2 Fenoxaprop-p-ethyl Technical (100% Basis) 8 20 15 8 5
3 Fomesafen Technical (100% Basis) 12.5 10 12.5 20 15
4 Safener (Mefenpyr diethyl) 2 4 3 2 1
5 Emulsifier (Blend of non-ionic and anionic ) 10 12 14 14 14
6 Co-solvent (NMP, butanol, vegetable oil, DMSO) 5 5 5 10 7
7 Solvent 1 (isophorone) 12 12 12 12 12
8 Solvent 2 (aromatic heavy naphtha, C-9, N,N-dimethyl decanamide, Cyclohexanone, isophorone etc.) Q.S.to
make
100% Q.S.to
make
100% Q.S.to
make
100% Q.S.to
make
100% Q.S.to
make
100%
Total 100 100 100 100 100
Q.S.: quantity sufficient required to make 100%) w/w formulation
Process of preparing synergistic Emulsifiable Concentrate (EC) herbicidal composition comprising Clethodim + Fenoxaprop-p-ethyl + Fomesafen
Table 4 provides quantities of active ingredients and raw material charged to prepare the synergistic composition of the present invention in Emulsifiable Concentrate (EC) form. In table 4, active ingredients Clethodim + Fenoxaprop-p-ethyl + Fomesafen are in technical grade form and their purity considered accordingly to make the formulation. Examples 6-10 of table 3 corresponds to column F-J in table 4.
Table 4: Quantities of active ingredients and raw material charged

s.
N. Ingredients Quantity (g)

F G H I J
1 Clethodim Technical (37% Basis) 32.44 27.03 32.44 29.73 35.14
2 Fenoxaprop-p-ethyl Technical (95% Basis) 08.43 21.06 15.79 08.43 05.27
3 Fomesafen Technical (95% Basis) 13.16 10.53 13.16 21.06 15.79
4 Mefenpyr diethyl 02.10 04.21 03.15 02.10 01.05
5 Emulsifier (Blend of non-ionic and anionic ) 10.00 12.00 14.00 14.00 14.00
6 Co-solvent (DMSO) 05.00 05.00 05.00 10.00 07.00
7 Solvent 1 (Isophorone) 12.00 12.00 12.00 12.00 12.00

8 Solvent 2 (aromatic heavy naphtha) 16.87 08.17 04.46 02.68 09.75
Total 100.00 100.00 100.00 100.00 100.00
The ingredients were weighed and taken as per table 4. The process followed is same as described in table 2 except herein fomesafen is used in place of oxyfluorfen.
Bio-efficacy of the herbicidal composition of the present invention Clethodim 12% + Fenoxaprop-p-ethyl 10% + Oxyfluorfen 10% EC
Experimental trial was conducted to evaluate the herbicidal composition of the present invention on two sites (site 1 and site 2) in India against major weeds in Soybean crop in two different variety (JS 9305 and JS 2069) with solo and binary formulations for comparison and ternary formulations of the present invention as per the details provided in Tables 5-14.
The experiment was laid out in Randomized Block Design (RBD). The plot size was 10 m x 10 m and the spacing was 30 cm x 10 cm. All the recommended agronomic practices were followed throughout the cropping period.
Observations from a composite sample (collected from three different spots in the experimental area) were recorded at 15, 30 and 45 days after herbicide application (DAHA). On each date of taking observation, weeds were collected from one square meter of each experimental plot and were cleaned. Weeds were then separated species wise and were oven dried and then weight was taken separately. Weed control efficacy (% WCE) for individual species was calculated using the formula:
W.C.E (%) = Weed population in control plot - weed population in treated plot X 100
Weed population in control plot
Yield: The Cumulative yield of soybean seed from individual plots leaving aside border rows were separately recorded and expressed in q ha"1.
Table 5: Treatment Details

S.N Treatments No. Treatment Details
1 Tl Clethodim 12% + Fenoxaprop-p-ethyl 10% + Oxyfluorfen 10% EC
2 T2 Clethodim 25% EC
3 T3 Fenoxaprop-p-Ethyl 9.3% EC

4 T4 Oxyflourfen 23.5% EC
5 T5 Clethodim 25% EC + Fenoxaprop-p-Ethyl 9.3% EC
6 T6 Clethodim 25% EC + Oxyflourfen 23.5% EC
7 T7 Fenoxaprop-p-Ethyl 9.3% EC + Oxyflourfen 23.5% EC
8 T8 Control
Table 6: Effect of treatment on weed control efficiency against Narrow Leaved weeds at different days after herbicides application

Trea
tmen
ts Dose 15 DAHA 30 DAHA 45 DAHA

Formul ation,
ml/ha a.i., g/ha Sitel Site 2 Pooled Sitel Site
2 Poole d Site 1 Site 2 Poole d
Tl 1000 120+ 100 + 100 83.43 82.05 82.74 80.56 79.9
2 80.24 76.1 0 75.45 75.78
T2 500 120 56.54 55.81 56.18 50.78 50.4 7 50.63 48.3 8 47.86 48.12
T3 1111 100 42.63 40.62 41.63 38.65 37.7
5 38.20 40.5 8 40.27 40.43
T4 425 100 22.25 22.15 22.20 18.04 17.1 1 17.58 17.2 4 15.29 16.27
T5 500 + 1111 120+ 100 72.94 71.99 72.47 65.00 63.5 9 64.30 61.4 4 59.83 60.63
T6 500 + 425 120+ 100 66.15 65.30 65.72 59.41 58.5
5 58.98 56.6 0 55.52 56.06
T7 1111 + 425 100+ 100 49.45 47.12 48.29 44.45 43.7 9 44.12 46.6
7 46.71 46.69
T8 - - - - - - - - - - -
Table 7: Effect of treatment on weed control efficiency against Broad Leaved weeds at different days after herbicides application

Tre atm ents I )ose 15 DAE [A 30 DAHA 4 [5 DAI HA

Form
ulatio
n
ml/ha a.i., g/ha Site 1 Site
2 Pooled Site 1 Site
2 Pooled Site 1 Site
2 Pooled
Tl 1000 120 + 100 + 100 76.9 3 74.86 75.90 72.7 0 69.6
5 71.18 73.8 0 70. 80 72.30
T2 500 120 23.7 5 23.44 23.59 21.3 3 21.2 0 21.26 20.3
2 20. 10 20.21
T3 1111 100 9.38 8.94 9.16 8.50 8.31 8.40 8.93 8.8 6 8.89
T4 425 100 52.7 3 52.50 52.61 42.7 5 40.5
5 41.65 40.8 6 36.
24 38.55
T5 500 + 1111 120 + 100 29.1
7 28.80 28.99 26.0 0 25.4 4 25.72 24.5 8 23. 93 24.25

T6 500 + 425 120 + 100 58.2 1 57.46 57.84 52.2 8 51.5
2 51.90 49.8 1 48. 86 49.33
T7 1111 +
425 100 + 100 54.8 9 52.30 53.60 48.0 0 46.4
2 47.21 44.3 3 43. 44 43.89
T8 - - - - - - - - - - -
Table 8: Effect of treatments on seed yield of Soybean crop at harvest

Treatments Dose Seed yield (q/ha) % increase against control

Formulation,
ml/ha a.i.,
g/ha Sitel Site 2 Mean

Ti 1000 120 + 100 + 100 9.58 8.91 9.25 62.62
T2 500 120 7.68 7.14 7.41 30.34
T3 1111 100 6.74 6.33 6.54 14.95
T4 425 100 7.26 6.89 7.08 24.45
T5 500 + 1111 120 + 100 7.98 7.42 7.70 35.44
T6 500 + 425 120 + 100 8.14 7.81 7.98 40.28
T7 1111 + 425 100 + 100 7.39 7.01 7.20 26.65
T8 - - 5.94 5.43 5.69 -
SEM 0.082 0.079 0.081 -
CD5% 0.252 0.242 0.247 -
SEM- Standard error of mean; CD5%: Critical Difference
Phytotoxicity Observations
For phytotoxicity evaluation at different doses of Clethodim 12% + Fenoxaprop-p-Ethyl 10%> + Oxyfluorfen 10%> EC, following observations were made by observing temporary or long lasting damage to the leaves, if any, viz., epinasty, hyponasty, necrosis, vein clearing and wilting at 15, 30 and 45 DAHA.
Table 9: Phyto-toxicity studies of treatments on Soybean crop

Tr
eat me nts No Treatments Detail Dose /ha Epinast
y Hyp
l lonas
ty Necrosis Vein clearing Wilting

Sit el Sit
e2 Sit el Site
2 Sit el Sit
e2 Sit el Sit
e2 Sit el Sit
e2
Ti Clethodim 12% + Fenoxaprop-p-ethyl 10% + Oxyfluorfen 10% EC 800 ml 0 0 0 0 0 0 0 0 0 0

T2 Clethodim 12% + Fenoxaprop-p-ethyl 10% + Oxyfluorfen 10% EC 1000 ml 0 0 0 0 0 0 0 0 0 0
T3 Clethodim 12% + Fenoxaprop-p-ethyl 10% +Oxyfluorfen 10% EC 1200 ml 0 0 0 0 0 0 0 0 0 0
T4 Clethodim 12% + Fenoxaprop-p-ethyl 10% +Oxyfluorfen 10% EC 1500 ml 0 0 0 0 0 0 0 0 0 0
T5 Clethodim 12% + Fenoxaprop-p-ethyl 10% +Oxyfluorfen 10% EC 2000 ml 0 0 0 0 0 0 0 0 0 0
T6 Control - 0 0 0 0 0 0 0 0 0 0
0-No Phyto-toxicity 10-Complete kill the plant
Clethodim 12% + Fenoxaprop-p-ethyl 8% +Fomesafen 12.5% EC
Experimental trial was conducted to evaluate the herbicidal composition of the present invention and all parameters are same as mentioned above. The observation and results are presented below in tables 10-14.
Table 10: Treatment Details

S.N Treatments No. Treatment Details
1 Tl Clethodim 12% + Fenoxaprop-p-ethyl 8% +Fomesafen 12.5% EC
2 T2 Clethodim 25% EC
3 T3 Fenoxaprop-p-Ethyl 9.3% EC
4 T4 Fomesafen22.5%SL
5 T5 Clethodim 25% EC + Fenoxaprop-p-Ethyl 9.3% EC
6 T6 Clethodim 25% EC + Fomesafen 22.5% SL
7 T7 Fenoxaprop-p-Ethyl 9.3% EC + Fomesafen 22.5% SL
8 T8 Control
Table 11: Effect of treatment on weed control efficiency against Narrow Leaved weeds at different days after herbicides application

Dose

15 DAHA

30 DAHA

45 DAHA

Tre atm ents Formulati
on, ml/ha a.i.,
g/ha Site 1 Site
2 Pooled Site 1 Site
2 Pooled Site 1 Site
2 Pooled
Tl 1000 120 + 80 + 125 82.1
2 81.6
7 81.90 79.2 6 78.4
2 78.84 76. 18 75.1 1 75.65
T2 500 120 56.5 4 55.8 1 56.18 50.7 8 50.4 7 50.63 48. 38 47.8 6 48.12
T3 889 80 30.3 0 29.2 4 29.77 27.8 1 27.0 9 27.45 26. 13 25.8
5 25.99
T4 500 125 17.8 0 16.9 3 17.37 16.1 0 15.3 0 15.70 15. 47 14.8 8 15.18
T5 500 + 889 120 + 80 66.2 8 65.0 3 65.66 62.8
5 61.9 3 62.39 59. 20 58.1 6 58.68
T6 500 + 500 120 + 125 53.5 8 52.9 1 53.25 48.1
2 47.4
2 47.77 45. 85 44.9
7 45.41
T7 889 + 500 80 + 125 28.4 7 27.6 7 28.07 25.9 1 25.4 7 25.69 24. 34 24.2 9 24.32
T8 - - - - - - - - - - -
Table 12: Effect of treatment on weed control efficiency against Broad Leaved weeds at different days after herbicides application

Tre atm ents Dose 15 DA] HA 30 DAHA 45 DAHA

Formulati
on, ml/ha a.i., g/ha Site 1 Site
2 Pooled Site 1 Site
2 Pooled Site 1 Site
2 Poole d
Tl 1000 120 + 80
+ 125 91.2
5 89.8 1 90.53 88.7 1 83.6 9 86.20 87. 80 82.4 8 85.14
T2 500 120 23.7 5 23.4 4 23.59 21.3 3 21.2 0 21.26 20.
32 20.1 0 20.21
T3 889 80 8.79 8.19 8.49 7.79 7.30 7.54 7.0 6 6.98 7.02
T4 500 125 68.7 1 65.3
5 67.03 63.7 6 60.5 9 62.17 63. 43 61.0 1 62.22
T5 500 + 889 120 + 80 28.1
7 26.8 6 27.52 25.2 8 24.3 1 24.80 23. 19 22.3 3 22.76
T6 500 + 500 120 + 125 72.2 6 70.9 4 71.60 68.3 9 67.5 9 67.99 66. 09 65.3
5 65.72
T7 889 + 500 80+ 125 67.2 0 65.9
7 66.59 63.6 0 62.8 6 63.23 61. 46 60.7 8 61.12
T8 - - - - - - - - - - -
Table 13: Effect of treatments on seed yield of Soybean crop at harvest

Treatments Dose seed yield (q/ha) % increase against control

Formulation,
ml/ha a.i.,
g/ha Sitel Site 2 Mean

SEM- Standard error of mean; CD5%: Critical Difference Phytotoxicity Observations
For phytotoxicity evaluation at different doses of Clethodim 12% + Fenoxaprop-p-Ethyl 8% + Fomesafen 12.5% EC, following observations were made by observing temporary or long lasting damage to the leaves, if any, viz., epinasty, hyponasty, necrosis, vein clearing and wilting at 15, 30 and 45 DAHA.
Table 14: Phyto-toxicity studies of treatments on Soybean crop
Ti 1000 120 + 80 + 125 9.96 9.34 9.65 69.74
T2 500 120 7.68 7.14 7.41 30.34
T3 889 80 6.51 6.06 6.29 10.55
T4 500 125 7.10 6.82 6.96 22.43
T5 500 + 889 120 + 80 7.82 7.39 7.61 33.77
T6 500 + 500 120+ 125 8.10 7.75 7.93 39.40
T7 889 + 500 80 + 125 7.14 6.98 7.06 24.19
T8 - - 5.94 5.43 5.69 -
SEM 0.092 0.089 0.091 _
CD5% 0.283 0.273 0.279 -

Tr
eat me nts No Treatments details Dose /ha Epinast
y Hyponas
Y Necrosis Vein clearing Wilting

Sit el Sit
e2 Sit el Sit
e2 Sit el Sit
e2 Sit el Sit
e2 Sit el Sit
e2
Ti Clethodim 12% + Fenoxaprop-p-ethyl 8%> +Fomesafen 12.5% EC 800 ml 0 0 0 0 0 0 0 0 0 0
T2 Clethodim 12% + Fenoxaprop-p-ethyl 8%> +Fomesafen 12.5% EC 1000 ml 0 0 0 0 0 0 0 0 0 0
T3 Clethodim 12% + Fenoxaprop-p-ethyl 8%> +Fomesafen 12.5% EC 1200 ml 0 0 0 0 0 0 0 0 0 0
T4 Clethodim 12% + Fenoxaprop-p-ethyl 8%> +Fomesafen 12.5% EC 1500 ml 0 0 0 0 0 0 0 0 0 0
T5 Clethodim 12% + Fenoxaprop-p-ethyl 2000 ml 0 0 0 0 0 0 0 0 0 0

8% +Fomesafen 12.5% EC
T6 Control - 0 0 0 0 0 0 0 0 0 0

0-No Phyto-toxicity

10-Complete kill the plant

Evaluation of synergistic effect
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. l(Jan 1967), pp. 20-2.
The synergistic action expected for a given combination of two active components can be calculated as follows:

E=(X+Y)

(XY) 100

The synergistic action expected for a given combination of three active components can be calculated as follows:
(XY+YZ+XZ) XYZ
E=(X+Y+Z) - — + -
100
10000
Where:
E represents expected percentage of control for the combination of the two/three active ingredients at defined doses (for example equal to x, y and z respectively),
X is the percentage of control observed by the compound (I) at a defined dose (equal to x),
Y is the percentage of control observed by the compound (II) at a defined dose (equal to y),
Z is the percentage of control observed by the compound (III) at a defined dose (equal to z).
If observed control of the combination > Expected control, the combination is synergistic If observed control of the combination < Expected control, the combination is antagonistic If observed control of the combination = Expected control, the combination is additive
Table 15: Synergistic effect of Clethodim 12% + Fenoxaprop-p-ethyl 10% + Oxyfluorfen 10% EC composition against Narrow Leaved weeds at different days after herbicides application

Dose 15 DAHA 30 DAHA 45 DAHA

rea tm ent No Dose
ml/ha a.i./
g/ha) Observ
ed
WCE
(%) #Expect
ed
WCE
(%) Observ
ed
WCE
(%) #Expect
ed
WCE
(%) Observe
d
WCE
(%) #Expect
ed
WCE
(%)
Ti 1000 120 +
100 +
100 82.74 80.10 80.24 74.85 75.78 74.12
T2 500 120 56.18 - 50.63 - 48.12 -
T3 1111 100 41.63 - 38.20 - 40.43 -
T4 425 100 22.20 - 17.58 - 16.27 -
T5 500 + 1111 120 + 10 72.47 74.42 64.30 69.49 60.63 69.10
T6 500 + 425 120 + 100 65.72 65.91 58.98 59.31 56.06 56.56
T7 1111 + 425 100 + 100 48.29 54.59 44.12 49.06 46.69 50.12
T8 - - - - - - - -
*For c ietails Refer •Table 5J t Calculate :d using Co by Formu a
Table 16: Synergistic effect of Clethodim 12% + Fenoxaprop-p-ethyl 10% + Oxyfluorfen 10% EC composition against Broad Leaved weeds at different days after herbicides application

15 DAHA 30 DAHA 45 DAHA
*Tr
eat
men
t
No. Dose ml/ha Dose
a.i./
g/ha Observ
ed
WCE
(%) #
Expecte d WCE
(%) Observ
ed
WCE
(%) #
Expecte d WCE
(%) Observe
d
WCE
(%) #
Expecte d WCE
(%)
Ti 1000 120 +
100 +
100 75.90 67.11 71.18 57.91 72.30 55.33
T2 500 120 23.59 - 21.26 - 20.21 -
T3 1111 100 9.16 - 8.40 - 8.89 -
T4 425 100 52.61 41.65 - 38.55 -
T5 500 + 1111 120 + 100 28.99 30.59 25.72 27.87 24.25 27.30

T6 500 + 425 120 + 100 57.84 63.79 51.90 54.06 49.33 50.97
T7 1111 + 425 100 + 100 53.60 56.95 47.21 46.55 43.89 44.01
T8 - - - - - -
*For de tails Refer Table 5. # Calculated using Co by Formu a
Table 17: Synergistic effect of Clethodim 12% + Fenoxaprop-p-ethyl 8% +Fomesafen 12.5% EC composition against Narrow Leaved weeds at different days after herbicides application

*Tr
eat
men
t
No. Dose ml/ha Dose a.i. g/ ha 15 DAHA 30 DAHA 45 DAHA

Observe
d
WCE
(%) #Expect
ed
WCE
(%) Observ
ed
WCE
(%) #Expect
ed
WCE
(%) Observe
d
WCE
(%) #Expect
ed
WCE
(%)
Ti 1000 120 + 80 + 125 81.90 74.57 78.84 69.81 75.65 67.43
T2 500 120 56.18 - 50.63 - 48.12 -
T3 889 80 29.77 - 27.45 - 25.99 -
T4 500 125 17.37 - 15.70 - 15.18 -
T5 500 + 889 120 + 80 65.66 69.23 62.39 64.18 58.68 61.60
T6 500 + 500 120 + 125 53.25 63.79 47.77 58.38 45.41 56
T7 889 + 500 80 + 125 28.07 41.97 25.69 38.84 24.32 37.22
T8 - - - - - - - -
*For details Refer Table 10. # Calculated using Colby Formula
Table 18: Synergistic effect of Clethodim 12% + Fenoxaprop-p-ethyl 8% +Fomesafen 12.5% EC composition against Broad Leaved weeds at different days after herbicides application

*Tr Dose Dose 15 DAHA 30 DAHA 45 DAHA
eat men ml/ha a.i.

Observ #Expecte Observ #Expecte Observ #Expecte
t ha ed d ed d ed d
No. WCE
(%) WCE (%) WCE
(%) WCE (%) WCE
(%) WCE (%)

Ti 1000 120 + 80
+ 125 90.53 76.95 86.20 72.46 85.14 71.97
T2 500 120 23.59 - 21.26 - 20.21 -
T3 889 80 8.49 - 7.54 - 7.02 -
T4 500 125 67.03 - 62.17 - 62.22 -
T5 500 + 889 120 + 80 27.52 30.08 24.80 27.20 22.76 25.81
T6 500 + 500 120
+ 125 71.60 74.81 67.99 70.21 65.72 69.86
T7 889 + 500 80 + 125 66.59 69.83 63.23 65.02 61.12 64.87
T8 - - - - - - - -
*For details Refer Table 10. # Calculated using Colby Formula
It is evident from table 15-18 that the observed weed control efficiency (% WCE) is more than the expected weed control efficiency (% WCE), hence, the composition of present invention is synergistic.
From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the 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.

We Claim:

1. A synergistic herbicidal composition comprising of:
a. Clethodim;
b. Fenoxaprop-p-ethyl;
c. at least one compound selected from Oxyfluorfen or Fomesafen; and
d. agriculturally acceptable additives.
2. The synergistic herbicidal composition as claimed in claim 1, comprising 10 to 20% w/w of Clethodim; 5 to 15% w/w of Fenoxaprop-p-ethyl; 5 to 25% w/w of Oxyfluorfen and agriculturally acceptable additives.
3. The synergistic herbicidal composition as claimed in claim 1, comprising 10 to 13% w/w of Clethodim; 5 to 20% w/w of Fenoxaprop-p-ethyl; 10-20%) w/w of Fomesafen and agriculturally acceptable additives.
4. The synergistic herbicidal composition as claimed in claim 2, comprising 12% w/w of Clethodim, 10% w/w of Fenoxaprop-p-ethyl; 10% w/w of Oxyfluorfen and agriculturally acceptable additives.
5. The synergistic herbicidal composition as claimed in claim 3, comprising 12% w/w of Clethodim, 8% w/w of Fenoxaprop-p-ethyl; 12.5% w/w of Fomesafen and agriculturally acceptable additives.
6. The synergistic herbicidal composition as claimed in claim 1, wherein the agriculturally acceptable additives is selected from the group comprising of:
a. emulsifiers present in an amount in the range from 1 to 20% w/w;
b. safeners present in an amount in the range from 0.1-5 % w/w; and
c. solvents present in an amount of quantity sufficient to make 100%)w/w formulation.
7. The synergistic herbicidal composition as claimed in claim 6, wherein:
a. the emulsifier is selected from the group comprising blend of non-ionic and anionic emulsifiers such as castor oil ethoxylates, alkoxylated alcohols, ethoxylated amines, ethoxylated tristyrylphenol, fatty acid ethoxylates, calcium salts of dodecylbenzene

sulphonate, salts of phosphate esters of ethoxylated tristyrylphenol, or a combination thereof;
b. the safener is selected from the group comprising benoxacor, cloquintocet mexyl,
cyprosulfamide, dichlormid, fenclorim, fenchlorazole, furilazole, isoxadifen,
mefenpyr, mefenpyr diethyl, naphthalic acid anhydride, 4-(dichloroacetyl)-l-oxa-4-
azaspiro[4.5]decane and 2,2,5-trimethyl-3- (dichloroacetyl)-l,3-oxazolidine or a
combination thereof;and
c. the solvent is selected from the group comprising butanol, glycol ether based solvent,
heavy aromatic naphtha, vegetable oils, decanamide, N-methyl-2-pyrrolidone,
isophorone, cyclohexanone, solvent C9 or a combination thereof.
8. The synergistic herbicidal composition as claimed in claim 1, wherein the composition is formulated as Emulsifiable Concentrate (EC).
9. The synergistic herbicidal composition as claimed in claim 1 or 8, wherein the composition is in Emulsifiable Concentrate (EC) form selected from a group comprising:
a. 12% w/w of Clethodim, 10% w/w of Fenoxaprop-p-ethyl, 10% w/w of Oxyfluorfen,
2% w/w of Mefenpyr diethyl, 10 % w/w of blend of non-ionic and anionic emulsifier,
10% w/w of isophorone, QS% w/w of heavy aromatic naphtha;
b. 20% w/w of Clethodim, 5% w/w of Fenoxaprop-p-ethyl, 5% w/w of Oxyfluorfen,
1%> w/w of Mefenpyr diethyl, 12 % w/w of blend of non-ionic and anionic emulsifier,
10%) w/w of isophorone, QS% w/w of heavy aromatic naphtha;
c. 10%> w/w of Clethodim, 12% w/w of Fenoxaprop-p-ethyl, 25% w/w of Oxyfluorfen,
2%> w/w of Mefenpyr diethyl, 14 % w/w of blend of non-ionic and anionic emulsifier,
10%) w/w of isophorone, QS% w/w of heavy aromatic naphtha;
d. 20%o w/w of Clethodim, 10% w/w of Fenoxaprop-p-ethyl, 10% w/w of Oxyfluorfen,
2%o w/w of Mefenpyr diethyl, 12 % w/w of blend of non-ionic and anionic emulsifier,
10%o w/w of isophorone, QS% w/w of heavy aromatic naphtha; and
e. 10%) w/w of Clethodim, 15% w/w of Fenoxaprop-p-ethyl, 20% w/w of Oxyfluorfen,
3%o w/w of Mefenpyr diethyl, 14 % w/w of blend of non-ionic and anionic emulsifier,
10%o w/w of isophorone, QS% w/w of heavy aromatic naphtha.

10. The synergistic herbicidal composition as claimed in claim 1 or 8, wherein the composition is in Emulsifiable Concentrate (EC) form selected from a group comprising:
a. 12%) w/w of Clethodim, 8%> w/w of Fenoxaprop-p-ethyl, 12.5% w/w of Fomesafen,
2%> w/w of Mefenpyr diethyl, 10 % w/w of blend of non-ionic and anionic emulsifier,
5%o w/w of dimethyl sulfoxide, 12% w/w of isophorone, QS% w/w of heavy aromatic
naphtha;
b. 10%o w/w of Clethodim, 20% w/w of Fenoxaprop-p-ethyl, 10% w/w of Fomesafen,
4%> w/w of Mefenpyr diethyl, 12 % w/w of blend of non-ionic and anionic emulsifier,
5%> w/w of dimethyl sulfoxide, 12%w/w of isophorone, QS% w/w of heavy aromatic
naphtha;
c. 12%) w/w of Clethodim, 15% w/w of Fenoxaprop-p-ethyl, 12.5% w/w of Fomesafen,
3%> w/w of Mefenpyr diethyl, 14 % w/w of blend of non-ionic and anionic emulsifier,
5%> w/w of dimethyl sulfoxide, 12%w/w of isophorone, QS% w/w of heavy aromatic
naphtha;
d. 11%> w/w of Clethodim, 8% w/w of Fenoxaprop-p-ethyl, 20% w/w of Fomesafen,
2%> w/w of Mefenpyr diethyl, 14 % w/w of blend of non-ionic and anionic emulsifier,
10%) w/w of dimethyl sulfoxide, 12%w/w of isophorone, QS% w/w of heavy
aromatic naphtha; and
e. 13%) w/w of Clethodim, 5% w/w of Fenoxaprop-p-ethyl, 15% w/w of Fomesafen,
1%> w/w of Mefenpyr diethyl, 14 % w/w of blend of non-ionic and anionic emulsifier,
7%> w/w of dimethyl sulfoxide, 12%w/w of isophorone, QS% w/w of heavy aromatic
naphtha.