DESC:FIELD OF THE INVENTION
The present invention relates to crop protection compositions, particularly a novel herbicidal composition, comprising Fenoxaprop ester, Acetolactate synthase (ALS) inhibitor and Fomesafen or its salts in combination and a process for preparing the same.
BACKGROUND OF THE INVENTION
Weeds are the plants that grow in fields where they compete with crops for water, soil nutrients, light and space and thus reducing crop yields. They harbour insect’s pests and micro-organisms. Control of weeds is an important aspect of agriculture. In common agricultural practice a great variety of herbicides are used to reduce adverse effects of weeds on crop production. A huge amount of cost is involved in control of weeds chemically by farmers all across the world. Herbicides are useful in controlling unwanted vegetation, i.e. weeds, which may otherwise cause significant damage to desirable plant species. Many potent herbicides have the ability to control for full growing seasons and at low rates of application. In order to reduce the adverse effect of weeds many herbicides have been combined into a single herbicidal composition. One method of preparing a composition is referred to as “tank mixing” wherein the ingredients in their commercially available form are mixed together by the end user, usually in a quantity of water. Tank mixing usually requires the user to store the commercial formulations, calculate the correct amount of each active ingredient and measure those amounts in to the mix. This also requires extra monitoring as the dosing of any active ingredient can result in development of resistance.
The present invention relates generally to crop protection compositions and, in one embodiment, to crop protection compositions containing fenoxaprop ester, acetolactate synthase (ALS) inhibitor and fomesafen or its salts in combination and uses thereof.
Herbicides from the abovementioned group of fenoxaprop ester are known from numerous documents. Thus, for example, the herbicidal action of numerous such compounds is described in U.S. Pat. Nos. 6,908,883 B2 and 6,887,827 B2. Some of the fenoxaprop ester mentioned therein exhibit a satisfactory herbicidal action against harmful plants occurring in different crops including cereals.
Fenoxaprop esters act as acetyl-CoA carboxylase inhibitors. An example of such herbicides includes fenoxaprop esters, such as fenoxaprop-p-ethyl that is commercially available from different sources. The IUPAC Name of Fenoxaprop-p-ethyl is (R)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionate and it is the herbicidally active R-enantiomer of the racemic substance fenoxaprop-ethyl. Fenoxaprop-P-ethyl is an odourless white solid. It is an aryloxyphenoxypropionate herbicide, used for post emergence control of annual grass weeds.
However, in practice, there are frequently disadvantages associated with use of the fenoxaprop ester known from these documents. Thus, the herbicidal activity is not always satisfactory or, with a satisfactory herbicidal activity, undesirable damage to the plants is observed.
The effectiveness of herbicides depends, inter alia, on the type of herbicide used, the application rate thereof, the composition, the harmful plants to be combated each time, the climatic and soil conditions, and the like. A further criterion is the duration of the action or the rate of degradation of the herbicide. Changes in the sensitivity of harmful plants to an active substance which may occur with relatively long use or in geographically restricted areas are also to be taken into account, if appropriate. Such changes are expressed as a more or less serious loss in activity and can only to a limited extent be compensated for by higher herbicide application rates.
Due to multitude of possible influencing factors, there is virtually no individual active substance which combines in itself the properties desired for different requirements, in particular with regard to the harmful plant species and the climatic zones. In addition, there is the constant problem of achieving the effect with an ever lower herbicide application rate. A lower application rate reduces not only the amount of an active substance required for the application but generally also reduces the amounts of formulation auxiliaries necessary. Both reduce the economic cost and improve the ecological compatibility of the herbicide treatment.
One method frequently used for improving the application profile of a herbicide consists in combining the active substance of one or more other active substances which contribute the additional properties desired. However, the combined use of several active substances not infrequently results in phenomena of physical and biological incompatibility, e.g. lack of stability of a combined formulation, decomposition of an active substance or antagonism of the active substances. On the other hand, what is desired are combinations of active substances with a favourable activity profile, high stability and the greatest possible synergistically strengthened activity which makes possible a reduction in the application rate in comparison with individual application of the active substances to be combined.
US 8673814 B2 and US 20140323299 A1 describe herbicidal mixtures of particular aryloxyphenoxypropionic esters with various herbicides. CA 2502743 A1 describes herbicidal mixtures of particular aryloxyphenoxypropionates with safeners. However, in practice, there are serious disadvantages to these mixtures. Thus, their compatibility with regard to useful plants, in particular cereals and oilseed crops, is not always satisfactory and their activity with regard to harmful plants is likewise not always satisfactory.
The present invention relates generally to herbicidal compositions or formulations, and to methods of using such compositions to kill, or control the growth and proliferation of, unwanted plants. In particular, the present invention relates to herbicidal compositions, as well as their methods of use, which comprise fenoxaprop ester, or a herbicidal derivative thereof; acetolactate synthase (ALS) inhibitor and fomesafen or their salts in combination and a process for preparing the same.

SUMMARY OF THE INVENTION
In accordance with an embodiment of the invention there is provided a synergistic herbicidal composition, comprising: a aryloxyphenoxypropionic ester; at least one acetolactate synthase (ALS) inhibitor, Fomesafen and additives.
In accordance with another embodiment of the invention, the aryloxyphenoxypropionic ester is Fenoxaprop ester.
In accordance with still another embodiment of the invention, the Fenoxaprop ester is Fenoxaprop-p-ethyl.
In accordance with still yet another embodiment of the invention, the ALS inhibitor is Chlorimuron ethyl.
Preferably, Fenoxaprop-p-ethyl, Chlorimuron ethyl and Fomesafen are present in ratios ranging from 5.0-10.0:0.6-0.9:12.5-15.0. Further, Fenoxaprop-p-ethyl is present in an amount of 5 to 10%, Fomesafen is present in an amount of 12.5 to 15% and Chlorimuron ethyl is present in an amount in the range from 0.60 to 0.90%.
The synergistic herbicidal composition may be in the form of a suspension concentrate (SC), water dispersible granules (WG) or soluble liquid (SL).
Preferably, the synergistic herbicidal composition of the present invention comprises additives selected from the group consisting of anti-freezing agent, dispersing cum wetting agent, defoamer, biocide, thickener, water and combinations thereof, and is in the form of a suspension concentrate (SC).
The synergistic herbicidal composition comprises the anti-freezing agent in an amount of 1.00-8.00%, preferably 5%, the dispersing cum wetting agent in an amount of 2.00-10.00%, preferably 5%, the defoamer in an amount of 0.01-0.50%, preferably 0.20%, the biocide in an amount of 0.01-0.50%, and preferably 0.20%, and the thickener is present in an amount of 0.10-0.50%, and preferably 0.15%.
In accordance with a further embodiment of the invention, the synergistic herbicidal composition of the present invention is non-phytotoxic.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1. is a flowchart for preparing a synergistic herbicidal composition in the form of a suspension concentrate (SC).
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a novel, stable and synergistic herbicidal combination. The novel combination of the present invention comprises combination of aryloxyphenoxypropionic ester, an ALS inhibitor, Fomesafen along with other additives.
The term "agrochemically effective amount" is that quantity of active agent, applied in any amount which will provide the required control of weeds. The particular amount is dependent upon many factors including, for example, the crop and weeds sought to be controlled and environmental conditions. The selection of the proper quantity of active agent to be applied, however, is within the expertise of one skilled in the art.
It is to be noted, as used in the specification and 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. The expression of various quantities in the terms of “% w/w” or “%” means the percentage by weight, relative to the weight of the total composition unless otherwise specified.
As used herein SL formulation, SC formulation and WG formulation are the international denominations adopted by the FAO (Food and Agriculture Organization of the United Nations) to designate soluble liquid, suspension concentrate and water dispersible granules, respectively.
It is an object of the present invention to provide herbicidal combinations, in particular for use in soybean crop, with improved properties in comparison with the state of the art.
Accordingly the inventors of the present invention, have formulated a synergistic herbicidal composition, comprising: a aryloxyphenoxypropionic ester; at least one acetolactate synthase (ALS) inhibitor; Fomesafen and additives.
Aryloxyphenoxypropionic esters typically act as acetyl-CoA carboxylase inhibitors. Examples include Fenoxaprop esters, such as Fenoxaprop-p-ethyl, commercially available from different sources. The Fenoxaprop esters, such as Fenoxaprop-p-ethyl, are particularly useful for application to cereal crops to combat grassy weeds.
The formula for Fenoxaprop-p-ethyl is shown below.

Non-limiting examples of aryloxyphenoxypropionic esters are described, for example, in U.S. Pat. Nos. 6,908,883 B2 and 6,887,827 B2. The present invention will be described with respect to the use of a Fenoxaprop ester, such as Fenoxaprop-p-ethyl, in an herbicide composition. However, it is to be understood that the invention is not limited to use with Fenoxaprop-p-ethyl but is believed to be applicable to other aryloxyphenoxypropionic esters, e.g., Fenoxaprop esters. In one non-limiting embodiment, the Fenoxaprop ester is Fenoxaprop-p-ethyl.
Fenoxaprop-p-ethyl is the common name used for (R)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionic acid; R-2-[4-(6-chlorobenzoxazol-2-yloxy)phenoxy]propionic acid and having chemical formula C18H16ClNO5 and belonging to aryloxyphenoxypropionic group of herbicides. Fenoxaprop-p-ethyl was reported by H. P. Huff et al. (Proc. Br. Crop Prot. Conf. –Weeds, 1989, 2, 717) and introduced by Hoechst AG (Now Bayer AG). Fenoxaprop-p-ethyl is commonly available in the market as Emulsifiable Concentrate (EC) formulation of different concentrations. In accordance with an aspect of the invention, Fenoxaprop-p-ethyl is present in an amount of 5 to 10% w/w.
According to another aspect of the present invention, ALS inhibitor herbicides include sulfonylureas such as rimsulfuron (DPX 9636), metsulfuron, metsulfuron-methyl, ethametsulfuron, nicosulfuron, triasulfuron, primisulfuron, bensulfuron, Chlorimuron, chorimuron-ethyl, chlorsulfuron, sulfometuron, thifensulfuron, tribenuron, triflusulfuron, clopyrasulfuron, and pyrazasulfuron; sulfonamides such as flumetsulam (DE498); and imidazolinones such as imazaquin, imazamethabenz, imazapyr, imazmethapyr and Imazethapyr.
Chlorimuron ethyl is the common name used for ethyl 2-(4-chloro-6-methoxypyrimidin-2-ylcarbamoylsulfamoyl) benzoate and having chemical formula C15H15ClN4O6S and belonging to sulfonylurea group of herbicides. It is represented by the following structural formula.

This was first described in US 4394506 and introduced in United States in 1986 by E.I. Dupont. Chlorimuron ethyl is commonly available in the market as 25 percent wettable powder (WP) formulation. In accordance with an aspect of the invention, Chlorimuron ethyl is present in an amount of 0.6-0.9% w/w.
Fomesafen is 5-(2-chloro-4-??,?,?-trifluoro-p-tolyloxy)-N-mesyl-2-nitrobenzamide having molecular formula C15H10ClF3N2O6S, molecular weight 438.8 and belonging to diphenyl ether group of herbicides. Its structure is as follows.

Fomesafen may occur both in protonated form and in the form of salts, e.g. in the form of a sodium salt. Where mention is made of the herbicides, all customary derivatives, for example as mentioned especially in the said 'The Pesticide Manual' or any other reference source, are to be considered part of the present disclosure. Fomesafen is mainly used for control of sedges and broad leaved weeds in oilseeds mainly soybean and ground nut. Fomesafen is commonly available in the market as 25 percent soluble liquid (SL) formulation. In accordance with an aspect of the invention, Fomesafen is present in an amount of 12.5-15% w/w.
Preferably, Fenoxaprop-p-ethyl, Chlorimuron ethyl and Fomesafen are present in ratios ranging from 5.0-10.0:0.6-0.9:12.5-15.0.
The synergistic herbicidal composition may be in the form of a suspension concentrate (SC), water dispersible granules (WG) or soluble liquid (SL).
The synergistic herbicidal composition, further comprises additives selected from the group consisting of anti-freezing agent, dispersing cum wetting agent, defoamer, biocide, thickener, water and combinations thereof, and the composition is in the form of a suspension concentrate (SC). The term “suspension concentrate” used herein refers to a suspension of the active herbicide and additives in a small quantity of liquid, usually water. A composition in the form of a suspension concentrate is user friendly and affords a reduced risk of occupational exposure.
An anti-freezing agent is generally added to herbicidal compositions, to prevent the aqueous compositions from freezing. Suitable anti-freezing agents useful herein include, but not limited to, propylene glycol, Diethylene glycol (DEG), Mono ethylene glycol (MEG) and combinations thereof. Preferably, the anti-freezing agent is present in an amount in the range from 1.00-8.00%, and more preferably 5.00%.
A dispersing cum wetting agent is another important component of a suspension concentrate as it facilitates the formation of a suspension of a water insoluble substrate in water. Non-limiting examples of dispersing cum wetting agents that can be used in the present invention include non-ionic surfactants and amine salt of phosphate tristyryl phenol ethylated, acrylic copolymer, ethoxylated polyarylphenol phosphate ester, each of which can be used individually or in combination, in an amount in the range from 2.00-10.00%, preferably 5%.
A defoamer, also called as anti-foam, is generally added to a herbicidal composition as foam formation prevents the efficient filling of a container. Preferably, the defoamer is dimethyl polysiloxane emulsion and present in an amount in the range from 0.01-0.50%, and more preferably 0.2%.
The synergistic herbicidal composition may contain a biocide selected from the group consisting of Proxel GXL, formaldehyde and combinations thereof, and present in an amount in the range from 0.01-0.50%, preferably 0.2%. Proxel GXL is a broad spectrum biocide for the preservation of industrial water-based products, such as the composition of the present invention, against spoilage from bacteria, yeasts and fungi.
It is necessary to add a thickener to a herbicidal composition to reduce the tendency of the herbicide composition to disperse when sprayed, and decrease the likelihood of it being rinsed off of the crops. Preferably, the synergistic herbicidal composition comprises xanthan gum as thickener in an amount in the range from 0.10-0.50%, and preferably 0.15%.
It has been surprisingly found that the synergistic herbicidal composition of present invention provides a wide spectrum control of weeds, delaying the emergence of the resistant strains of weeds, and achieving effective and economical control of undesired weeds.
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 reagents used in the examples were obtained or are available from the chemical suppliers.

EXAMPLES
Examples 1 to 4:
The unit of each value below is “% w/w” i. e. the percentage by weight, relative to the weight of the total solution or composition unless otherwise specified. The compositions illustrated in Table 1 are formulated as a suspension concentrate (SC) formulation.
Table 1: Synergistic herbicidal composition
No. Component Function Example (%)
1 2 3 4
1 Fenoxaprop-p-Ethyl A.I. 5.00 10.00 5.00 10.00
2 Chlorimuron Ethyl A.I. 0.60 0.60 0.90 0.90
3 Fomesafen A.I. 15.00 12.50 15.00 12.50
4 Propylene glycol Anti-freezing agent 5.00 5.00 5.00 5.00
5 Amine salt of phosphate tristyryl phenol ethylated Dispersing cum Wetting Agent 5.00 5.00 5.00 5.00
6 Dimethyl Polysiloxane emulsion Defoamer 0.20 0.20 0.20 0.20
7 Proxel GXL Biocide 0.20 0.20 0.20 0.20
8 Xanthan Gum Thickener 0.15 0.15 0.15 0.15
9 D.M. Water Solvent Q.S. Q.S. Q.S. Q.S.
A.I.= active ingredient
Q.S.= quantity sufficient
D.M.= demineralized water
The aforementioned herbicidal composition can be formulated as suspension concentrate (SC) by the process described below.
Process for preparing synergistic herbicidal composition in the form of Suspension Concentrate (SC):
The synergistic herbicidal compositions of Examples 1 to 4 are prepared by the process depicted in Figure 1. All the raw materials were verified for conformance to the laid down individual specifications. The raw materials required for preparing compositions of examples 1 to 4 are illustrated in table 2 under the column headings 1 to 4 respectively. Entries for Fenoxaprop-p-ethyl, Chlorimuron ethyl and Fomesafen in table 2 differ from those in table 1 as entries in table 1 are for 100% pure compounds, whereas those in table 2 are for technical ones, i.e. those containing a certain percentage of impurities.
The amounts of active ingredients presented in table 2 may be greater than the values calculated taking into account the percentage purity of the active ingredients, to compensate for losses of said ingredients during the manufacturing process. It was observed that following said procedure on industrial scale the final yield of A.I. will be similar or same as to standardized values.
The required quantities of raw materials as illustrated in Table 2 below, were weighed, and transferred through the auto-batching system. The dispersing cum wetting agent is first diluted in demineralized (D.M.) water and solubilized by high shear mixing, and then added along with required quantities of anti-freezing agent, Fenoxaprop ethyl technical, Chlorimuron ethyl technical, defoamer and Fomesafen technical, into a premixing vessel, to make a homogeneous mass. Thereafter, the homogenous mass was ground to a mean particle size of 3-5 microns in a bead mil and mixed with 2% aqueous solution of xanthan gum under low stirring. Further, the quality of in-process sample was checked for conformance to the laid out specifications. Finally, the quality approved in-process sample was transferred to the holding tank after passing through sparkler filter pump for packing as per the requirements.
Table 2: Quantities of the *TGAI and raw materials charged
Component Function Quantities of materials charged (kg)
1 2 3 4
Fenoxaprop-p-Ethyl (based on 95% w/w minimum purity) *TGAI 5.27 10.53 5.27 10.53
Chlorimuron Ethyl (based on 95% w/w minimum purity) *TGAI 0.64 0.64 0.95 0.95
Fomesafen (based on 95% w/w minimum purity) *TGAI 15.79 13.16 15.79 13.16
Propylene glycol Anti-freezing agent 5.00 5.00 5.00 5.00
Amine salt of phosphate tristyryl phenol ethylated Dispersing cum Wetting Agent 5.00 5.00 5.00 5.00
Dimethyl Polysiloxane emulsion Defoamer 0.20 0.20 0.20 0.20
Proxel GXL Biocide 0.20 0.20 0.20 0.20
Xanthan Gum Thickener 0.15 0.15 0.15 0.15
D.M. Water Solvent 67.75 65.12 67.44 64.81
*Technical grade active agent
Evaluation of bio-efficacy of synergistic herbicidal composition against weed spectrum in soybean crop
Field tests of the compositions according to the present invention were conducted at various controlled trial sites. The performance of the herbicidal composition according to the present invention (Fenoxaprop-p-ethyl, Chlorimuron Ethyl and Fomesafen) was compared against the known compositions of Fenoxaprop-p-ethyl 9.3% EC, Chlorimuron Ethyl 25% WP and Fomesafen 25% SL, which were evaluated against target weeds. Application was made using high volume knapsack sprayer at 2-3 weed leaf stage. Observation on weed population, dry weight and weed control efficiency (WCE%) was assessed at 30 days after application (DAA).
Table 3 below summarizes the synergistic effect that exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components against different weed spectrum at different concentrations.
In the field of agriculture, it is often understood that the term "synergy" is as defined by Colby S. R. in an article entitled "Calculation of the synergistic and antagonistic responses of herbicide combinations" published in the journal Weeds, 1967, 15, p. 20-22. The action expected for a given combination of three active components can be calculated as follows:

Where,
E = Expected percentage of herbicidal control for the combination of the two herbicides at defined doses (for example equal to x and y respectively),
X = X is the percentage of herbicidal control observed by the compound (I) at a defined dose (equal to x),
Y = Y is the percentage of herbicidal control observed by the compound (II) at a defined dose (equal to y),
Z = Z is the percentage of herbicidal control observed by the compound (III) at a defined dose (equal to z),
When the percentage of herbicidal control observed for the combination is greater than the expected percentage, there is a synergistic effect.
Table 3: Synergistic impact of separate and combined treatments for overall weed spectrum at different concentrations of synergistic herbicidal composition
Compound A.I./ha
WCE (%) at 30 DAA* Expected Control (Et) Colby’s Ratio (Ea+b/Et)
Fenoxaprop-p-ethyl 50 Ea = 26.47 - -
Fenoxaprop-p-ethyl 100 Ea1 = 36.42 - -
Chlorimuron Ethyl 6 Eb = 37.81 - -
Chlorimuron Ethyl 9 Eb1 = 46.61 - -
Fomesafen 125 Ec = 35.68 - -
Fomesafen 150 Ec1 = 39.24 - -
Fenoxaprop-p-ethyl + Chlorimuron Ethyl + Fomesafen 50 + 6 + 150 Ea+b+c1 = 78.56 64.25 1.22
Fenoxaprop-p-ethyl + Chlorimuron Ethyl + Fomesafen 100 + 6 + 125 Ea1+b+c = 84.59 60.78 1.39
Fenoxaprop-p-ethyl + Chlorimuron Ethyl + Fomesafen 50 + 9 + 150 Ea+b1+c1 = 80.43 63.91 1.26
Fenoxaprop-p-ethyl + Chlorimuron Ethyl + Fomesafen 100 + 9 + 125 Ea1+b1+c = 84.04 58.14 1.44
DAA = Days after application
Ea = % WCE after 30 DAA for Fenoxaprop-p-ethyl
Eb = % WCE after 30 DAA for Chlorimuron Ethyl
Ec = % WCE after 30 DAA for Fomesafen
Ea+b+c = % WCE after 30 DAA for Fenoxaprop-p-ethyl + Chlorimuron Ethyl + Fomesafen
Et = Expected %WCE after 30 DAA for Fenoxaprop-p-ethyl + Chlorimuron Ethyl + Fomesafen in combination from alone
It can be seen from the data presented in Table 3 that combination of Fenoxaprop-p-ethyl, Chlorimuron Ethyl and Fomesafen demonstrate synergistic effect against different weed population at all the different doses tested.
Bio-efficacy of synergistic herbicidal composition against weed spectrum in soybean (Glycine max) crop
Field trials were performed to evaluate the biological efficacy of the synergistic herbicidal composition of present invention against the commonly occurring weed spectrum in soybean (Glycine max) crop. This evaluation was performed by comparing the claimed novel herbicidal composition in the present specification against the known compositions, i.e., Fenoxaprop-p-Ethyl 9.3% EC; Chlorimuron Ethyl 25% WP and Fomesafen 25% SL.
Observation on weed population, dry weight and weed control efficiency (WCE %) was calculated by throwing square quadrant randomly in the trial plots and calculating the number of weeds based on type of weeds before the spray and 45 days after application (DAA) of the spray. Area for experiment was marked for different plot sizes and application was made using high volume knapsack sprayer at 20 days after sowing (DAS). Based on various doses, weighed quantity of test products were dissolved in 5 liter of water/treatment and sprayed uniformly. All the recommended agronomic practices are followed as per good agriculture practices (GAP) including the use of recommended insecticides and fungicides for control of insect pest and diseases. Experimental design was in randomized blocks with seven replication and each plot measured an area of 100 sq. m (10 m × 10 m).
Details of Experiment
Target weeds: Annual and perennial grasses, sedges and broad leaved weeds
Crop: Soybean (Glycine max)
Application Method: high volume knapsack sprayer fitted with flat fan nozzle
The treatment details are tabulated in Table 4 below.
Table 4: Treatment details for evaluation of bio-efficacy of new herbicide against weed spectrum in Soybean (Glycine max)
Particulars Treatment Dose /ha Dose a.i./ha (g/ha) Time of Application
T1 Fenoxaprop-p-Ethyl 10% + Chlorimuron Ethyl 0.6% + Fomesafen 12.5% SC 1000 mL 100 + 6 + 125 15 DAS
T2 1200 mL 120 + 7.2 + 150
T3 Fenoxaprop-p-Ethyl 10% + Chlorimuron Ethyl 0.9% + Fomesafen 12.5% SC 1000 mL 100 + 9 + 125
T4 1200 mL 120 + 11.8 + 150
T5 Fenoxaprop-p-Ethyl 9.3% EC 625 mL 56.25
T6 Chlorimuron Ethyl 25% WP 36 g 9
T7 Fomesafen 25% SL 1000 mL 250
T8 Control (Water Spray) -- --
The bio-efficacy effect of different treatment schedules on soybean crop and the treatment wise yield data of soybean is summarized in Tables 5 and 6 below.

Table 5: Effect of synergistic herbicidal composition on total weed count (no./m2), total weed dry weight (g/m2) and weed control efficacy (WCE) (%) in Soybean (Glycine max) at 45 DAA (Days After Application)
No. Treatments Dose per acre Weed Population (no./m2) Weed Dry Weight (g/m2) Weed Control Efficacy (%)
Narrow leaved Sedges Broad leaved Total Weed Count
1 T1 1000 mL 3.67
(2.04) 1.29
(1.33) 3.50
(2.00) 8.46
(2.99) 11.53
(3.46) 70.00
2 T2 1200 mL 1.18
(1.29) 1.00
(1.22) 2.67
(1.78) 4.85
(2.31) 7.81
(2.88) 79.68
3 T3 1000 mL 3.33
(1.96) 1.40
(1.37) 3.18
(1.91) 7.91
(2.90) 10.21
(3.27) 73.44
4 T4 1200 mL 1.33
(1.35) 0.71
(1.10) 2.76
(1.80) 4.80
(2.30) 7.09
(2.75) 81.56
5 T5 625 mL 7.13
(2.76) 2.50
(1.73) 8.63
(3.02) 18.26
(4.33) 28.45
(5.38) 25.98
6 T6 36 g 9.00
(3.08) 2.67
(1.63) 4.59
(2.26) 16.26
(4.09) 22.39
(4.78) 41.75
7 T7 1000 mL 14.67
(3.89) 4.33
(2.19) 4.00
(2.12) 23.00
(4.79) 20.66
(4.60) 46.25
8 T8 -- 17.33
(4.22) 6.83
(2.70) 10.33
(3.29) 34.49
(5.91) 38.44
(6.24) --

SEm+ - 0.220 0.153 0.116 0.304 0.335 -
CD 5% - 0.678 0.471 0.357 0.937 1.032 -
DAA: Days after application; CD 5%: Critical Difference; g = Gram; m2 = Square meter; mL = Millilitre, g = Gram * Value in parenthesis is square root transformed values

Table 6: Treatment wise seed yield data in Soybean (Glycine max)
Treatment Seed yield
(q/ ha)
T1 32.00
T2 32.80
T3 32.54
T4 33.15
T5 23.33
T6 25.45
T7 27.00
T8 19.00
SEm+ 1.67
CD 5% 5.15
CD 5%: Critical Difference, q/ha = quintal per hectare
Data presented in table 5 shows that weed population was significantly affected by all the treatments compared to control when observed at 45 days after application (DAA). At 45 DAA synergistic herbicide composition @ all the doses recorded lowest weed population in comparison to known compositions. Similar results were observed in case of Weed dry weight, WCE and yield.

Phytotoxic effect of synergistic herbicidal composition on soybean (Glycine max)
Visual observation on phytotoxicity were recorded for leaf injury on tip/surface, Epinasty/Hyponasty, and wilting, etc. on 0-10 scale (table 7) at 1, 3, 7, 14 and 21 days after each application and the average values are presented in table 8.
Table 7. Phytotoxicity visual scoring 0-10
Score Phytotoxicity (percent)
0 No phytotoxicity
1 1 – 10
2 11 – 20
3 21 – 30
4 31 – 40
5 41 – 50
6 51 – 60
7 61 – 70
8 71 – 80
9 & 10 Complete destruction
Table 8: Phytotoxicity of synergistic herbicidal composition on Soybean (Glycine max)
No. Treatments Dose (mL/ha) Phytotoxicity (Days after Application)
1 3 7 14 21
1 Fenoxaprop-p-Ethyl 10% + Chlorimuron Ethyl 0.6% + Fomesafen 12.5% SC 1000 0 0 0 0 0
2 2000 0 0 0 0 0
3 3000 0 0 0 0 0
4 4000 0 0 0 0 0
5 Fenoxaprop-p-Ethyl 10% + Chlorimuron Ethyl 0.9% + Fomesafen 12.5% SC 1000 0 0 0 0 0
6 2000 0 0 0 0 0
7 3000 0 0 0 0 0
8 4000 0 0 0 0 0
9 Control - 0 0 0 0 0
0= No Phytoxicity
Table 8 above shows that the novel herbicidal composition comprising Fenoxaprop-p-ethyl, Chlorimuron ethyl (ALS Inhibitors) and Fomesafen did not show any phytotoxicity even at higher dose of 4000 mL/ha in Soybean (Glycine max).
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 investigation. It is to be understood that no limitations with respect to the specific aspect 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.

CLAIMS:
We claim:
1. A synergistic herbicidal composition, comprising: a aryloxyphenoxypropionic ester; at least one acetolactate synthase (ALS) inhibitor; Fomesafen and additives.
2. The synergistic herbicidal composition, as claimed in claim 1, wherein the aryloxyphenoxypropionic ester is Fenoxaprop ester.
3. The synergistic herbicidal composition, as claimed in claim 2, wherein the Fenoxaprop ester is Fenoxaprop-p-ethyl.
4. The synergistic herbicidal composition, as claimed in claims 1 to 3, wherein the ALS inhibitor is selected from the group consisting of: (a) sulfonylureas such as rimsulfuron (DPX 9636), metsulfuron, metsulfuron-methyl, ethametsulfuron, nicosulfuron, triasulfuron, primisulfuron, bensulfuron, Chlorimuron, chorimuron-ethyl, chlorsulfuron, sulfometuron, thifensulfuron, tribenuron, triflusulfuron, clopyrasulfuron, and pyrazasulfuron; b) sulfonamides such as flumetsulam (DE498); and c) imidazolinones such as imazaquin, imazamethabenz, imazapyr, imazmethapyr and Imazethapyr.
5. The synergistic herbicidal composition; as claimed in claims 1 to 4, wherein the ALS inhibitor is Chlorimuron ethyl.
6. The synergistic herbicidal composition as claimed in claims 4 and 5, wherein Fenoxaprop-p-ethyl, Chlorimuron ethyl and Fomesafen are present in a ratios ranging from 5.0-10.0:0.6-0.9:12.5-15.0.
7. The synergistic herbicidal composition, as claimed in claims 4, 5 and 6, wherein Fenoxaprop-p-ethyl is present in an amount of 5 to 10%, Fomesafen is present in an amount of 12.5 to 15% and Chlorimuron ethyl is present in an amount in the range from 0.60 to 0.90%.
8. The synergistic herbicidal composition, as claimed in claims 1 to 7, wherein the composition may be in the form of a suspension concentrate (SC), water dispersible granules (WG) or soluble liquid (SL).
9. The synergistic herbicidal composition, as claimed in claims 1 to 8, wherein the additives are selected from the group consisting of anti-freezing agent, dispersing cum wetting agent, defoamer, biocide, thickener, water and combinations thereof, and the composition is in the form of a suspension concentrate (SC).
10. The synergistic herbicidal composition, as claimed in claim 9, wherein the anti-freezing agent is selected from the group consisting of propylene glycol, di-ethylene glycol (DEG), mono-ethylene glycol (MEG) and combinations thereof, and present in an amount in the range from 1.00-8.00% and preferably 5%.
11. The synergistic herbicidal composition, as claimed in claim 9, wherein the dispersing cum wetting agent is selected from the group consisting of mixture of non-ionic surfactants and amine salt of phosphate tristyryl phenol ethylated, acrylic copolymer, ethoxylated polyarylphenol phosphate ester and combinations thereof, and present in an amount in the range from 2.00-10.00%, preferably 5%.
12. The synergistic herbicidal composition, as claimed in claim 9, wherein the defoamer is dimethyl polysiloxane emulsion and present in an amount in the range from 0.01-0.50%, and preferably 0.20%.
13. The synergistic herbicidal composition, as claimed in claim 9, wherein the biocide is selected from Proxel GXL or formaldehyde and present in an amount in the range from 0.01-0.50%, and preferably 0.20%.
14. The synergistic herbicidal composition, as claimed in claim 9, wherein the thickener is Xanthan gum and present in an amount in the range from 0.10-0.50%, and preferably 0.15%.

15. The synergistic herbicidal composition, as claimed in any of the claims 1 to 14, wherein said composition is non-phytotoxic.