DESC:FORM 2

THE PATENTS ACT, 1970
(SECTION 39 OF 1970)
&
The Patents Rules, 2003

COMPLETE SPECIFICATION
(Section 10 and Rule 13)

SYNERGISTIC PHENOXY HERBICIDAL COMBINATION FORMULATIONs, PROCESS FOR PREPARING AND USE THEREOF

We, COROMANDEL INTERNATIONAL LIMITED,
an Indian company incorporated under Companies Act of 1956, having its principal place of business 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 synergistic herbicidal composition comprising combination of a phenoxy herbicide and imidazolinone herbicide.

The present invention also relates to synergistic herbicidal composition comprising combination of a phenoxy herbicide, imidazolinone herbicide and other agrochemical auxiliaries.

The present invention also relates to synergistic herbicidal composition comprising combination of a phenoxy herbicide, imidazolinone herbicide, an emulsifier and other agrochemical auxiliaries, wherein said phenoxy herbicide is selected from Fenoxaprop-P-ethyl and Clodinafop-propargyl, said imidazolinone herbicide is Imazethapyr.

The present invention specifically relates to synergistic herbicidal composition comprising combination of Fenoxaprop-P-ethyl, Imazethapyr and agrochemical auxiliaries.

The present invention specifically relates to synergistic herbicidal composition comprising combination of Clodinafop-propargyl, Imazethapyr and agrochemical auxiliaries.

The present invention specifically relates to synergistic herbicidal composition comprising combination of phenoxy herbicide, imidazolinone herbicide at a weight in the ratio of 1 : 10 to 10 : 1 of first active ingredient to the second active ingredient, more preferably in the ratio of 1 : 5 to 5 : 1.

The present invention also relates to a process for the preparation of synergistic herbicidal composition comprising combination of phenoxy herbicide and imidazolinone herbicide, wherein the composition is prepared by simple blending and mixing and filtering process.

BACKGROUND OF THE INVENTION
Phenoxy herbicides (or "phenoxies") are a family of chemicals related to the growth hormone indoleacetic acid (IAA). When sprayed on broad-leaf plants they induce rapid, uncontrolled growth ("growing to death"). When sprayed on monocotyledonous (grass) crops such as wheat or corn, they selectively kill broad-leaf weeds, leaving the crops relatively unaffected. The wide variety of phenoxies in use today can be grouped into the phenoxyacetic, phenoxybutyric and phenoxypropionic subtypes, the latter containing the aryloxyphenoxypropionic subtype with the greatest number of commercial variants. Chemically, they are carboxylic acids, typically applied in an ester or salt form.

Fenoxaprop-P-ethyl is used as a selective, systemic herbicide against annual monocotyledon weeds such as field foxtail grass, flying oats, millet species and wind stalks, especially in cereal cultivation. In the cultivation of grain and rice, Fenoxaprop is applied together with the safener Mefenpyr-diethyl (partly also Cloquintocet-mexyl). In dicotyledonous crops such as soybeans, beets, potatoes or rapeseed, it can also be used without a safener.

Fenoxaprop-P-ethyl is an ester that is quickly hydrolyzed to acid, the actual active ingredient, in sensitive plants. It works by inhibiting acetyl-CoA carboxylase (ACCase) in fatty acid biosynthesis.

Fenoxaprop-P-ethyl is chemically known as ethyl (2R)-2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}propanoate and has the following structure:

US 4,130,413 A claims Fenoxaprop-P-ethyl generically.

Clodinafop-propargyl is a member of the aryloxyphenoxy propionate chemical family. It acts as a systemic herbicide that acts on post-emergent weeds such as selected grasses. It does not act on broad leaved weeds. It is applied to the foliar parts of the weeds and is absorbed through the leaves. This foliar acting grass weed killer is translocated to the meristematic growing points of the plant where it interferes with the production of fatty acids required for plant growth. Grass weeds controlled include wild oats, rough meadow-grass, green foxtail, barnyard grass, persian darnel, volunteer canary seed. It also provides moderate control of Italian rye-grass. It is suitable for use on the following crops – all varieties of wheat, autumn-sown spring wheat, rye, triticale and durum wheat.

Clodinafop-propargyl is chemically known as 2-propynyl (2R)-2-[4-[(5-chloro-3-fluoro-2-pyridinyl)oxy]phenoxy]propanoate and has the following structure:

US 4,713,109 A claims Clodinafop-propargyl product

Imazethapyr is an imidazole compound used as a selective herbicide. It is applied preplant incorporated, preemergence, at cracking, and postemergence. The compound controls weeds by reducing the levels of three branched-chain aliphatic amino acids, isoleucine, leucine and valine, through the inhibition of aceto-hydroxyacid synthase, an enzyme common to the biosynthetic pathway for these amino acids. This inhibition causes a disruption in protein synthesis which, in turn, leads to an interference in DNA synthesis and cell growth. The compound is used to control grasses and broadleaved weeds including barnyardgrass, crabgrass, cocklebur, panicums, pigweeds, nightshade, mustard, smartweed, velvetleaf, jimsonweed, foxtails, seedling johnsongrass, lambsquarters, morningglory and others. Tolerant crops include soybeans, peanuts, dry and edible beans, peas, alfalfa and imidazolinone resistant/tolerant corn. Additional research is being conducted on other leguminous crops.

Imazethapyr is chemically, 2-[4.5-dihydro-4-methyl-4-(1 -methylethyl)-5-oxo-lH-imidazol-2-yl]-5-ethyl-3-pyridinecarboxylic acid and has the following structure:

US 4,798,619 A claims Imazethapyr generically.

The combinations with herbicidal / pesticidal active substances for widening the spectrum of action and/or for protecting the crop plants are also known. Though, the ability of these combination compounds to efficiently control diseases varies with a large number of the parameters including, but not limited, the type of the formulations of combination fungicide, the type of phytopathogenic fungi to be controlled, the type of the plant to be protected and ambient conditions, such as temperature, precipitations, humidity, length of the day, biological diversity of the micro environment, the like.

Though, conventionally each of these Active ingredients are used individually, combination product is not approved which has applications compared to the mono product. Hence, there is increased interest in the use of Active ingredients in combination to give synergistic results.

Therefore, formulations of fungicidal active substances in combinations should generally have good chemical and physical stability, good application properties, user friendliness, having good biological activity and enhanced efficacy combined with high selectivity. Proper formulation and efficient delivery systems of combinations fungicides are the key elements in the performance of different products.

Accordingly, there is a need in the art to provide herbicidal synergistic compositions which are environmentally safer and stable herbicidal compositions having two active ingredients with different physical and chemical properties, which are environmentally safe, easy and effective combination formulation of two active with enhanced efficacy and stable product during storage.

It was surprisingly and unexpectedly found by the present inventors that a selective combination composition of two active ingredients comprising phenoxy herbicide and imidazolinone herbicide and other agrochemical auxiliaries, possesses enhanced efficacy, improved penetration and long duration control of phytopathogens as compared to its other traditional formulations with long storage stability across a wide temperature range and having no adverse impact on photosynthetic activity in plant and seed quality.

OBJECTIVE OF INVENTION
The main objective of the present invention is to provide synergistic herbicidal composition comprising combination of a phenoxy herbicide and imidazolinone herbicide.

Another objective of the present invention is to provide synergistic herbicidal composition comprising combination of a phenoxy herbicide, imidazolinone herbicide and other agrochemical auxiliaries.

Another objective of the present invention is to provide synergistic herbicidal composition comprising combination of a phenoxy herbicide, imidazolinone herbicide, an emulsifier and other agrochemical auxiliaries, wherein said phenoxy herbicide is selected from Fenoxaprop-P-ethyl and Clodinafop-propargyl, said imidazolinone herbicide is Imazethapyr.

Another objective of the present invention is to provide synergistic herbicidal composition comprising combination of Fenoxaprop-P-ethyl, Imazethapyr and agrochemical auxiliaries.

Another objective of the present invention is to provide synergistic herbicidal composition comprising combination of Clodinafop-propargyl, Imazethapyr and agrochemical auxiliaries.

Another objective of the present invention is to provide synergistic herbicidal composition comprising combination of phenoxy herbicide, imidazolinone herbicide at a weight in the ratio of 1 : 10 to 10 : 1 of first active ingredient to the second active ingredient, more preferably in the ratio of 1 : 5 to 5 : 1.

Another objective of the present invention is to provide a process for the preparation of synergistic herbicidal composition comprises combination of phenoxy herbicide and imidazolinone herbicide, wherein the composition is prepared by simple blending, mixing and filtering process.

SUMMARY OF INVENTION
Accordingly, the present invention provides a synergistic herbicidal composition comprising combination of a phenoxy herbicide and imidazolinone herbicide.

In one embodiment, the present invention provides a synergistic herbicidal composition comprising combination of a phenoxy herbicide, imidazolinone herbicide and other agrochemical auxiliaries.

In another embodiment, the present invention provides a synergistic herbicidal composition comprising combination of a phenoxy herbicide, imidazolinone herbicide, an emulsifier and other agrochemical auxiliaries.

In another embodiment, the present invention provides a synergistic herbicidal composition comprising combination of a phenoxy herbicide, imidazolinone herbicide, an emulsifier and other agrochemical auxiliaries, wherein said phenoxy herbicide is selected from Fenoxaprop-P-ethyl and Clodinafop-propargyl, said imidazolinone herbicide is Imazethapyr.

In another embodiment, the present invention provides a synergistic herbicidal composition comprising:
a) Fenoxaprop-P-ethyl,
b) Imazethapyr, and
c) agrochemical auxiliaries.

In another embodiment, the present invention provides a synergistic herbicidal composition comprising:
a) Clodinafop-propargyl,
b) Imazethapyr, and
c) agrochemical auxiliaries.

In another embodiment, the present invention provides a synergistic herbicidal composition comprising combination of phenoxy herbicide, imidazolinone herbicide at a weight in the ratio of 1 : 10 to 10 : 1 of first active ingredient to the second active ingredient, more preferably in the ratio of 1 : 5 to 5 : 1.

In another embodiment, the present invention provides a synergistic herbicidal composition comprising combination of a phenoxy herbicide, imidazolinone herbicide, an emulsifier and other agrochemical auxiliaries, wherein said composition is in the form of Emulsifiable concentrate (EC) or Soluble concentrates (SL).
In another embodiment, the present invention provides a synergistic herbicidal composition comprising:
a) phenoxy herbicide selected from Fenoxaprop-P-ethyl and Clodinafop-propargyl,
b) Imazethapyr,
c) emulsifiers, and
d) other agrochemical auxiliaries.

In another embodiment, the present invention provides a synergistic herbicidal composition comprising:
a) phenoxy herbicide selected from Fenoxaprop-P-ethyl and Clodinafop-propargyl in the range of 1% to 30% (w/w),
b) Imazethapyr in the range of 1% to 30% (w/w),
c) emulsifiers in the range of 1% to 30% (w/w), and
d) other agrochemical auxiliaries in the range of 0.1% to 80% (w/w).

In another embodiment, the present invention provides a synergistic herbicidal composition comprising combination of a phenoxy herbicide, imidazolinone herbicide, an emulsifier and other agrochemical auxiliaries, wherein said other agrochemical auxiliaries are selected from stabiliser and solvents.

In another embodiment, the present invention provides an emulsifiable concentrate composition comprising:
a) Fenoxaprop-P-ethyl in the range of 1% to 30% (w/w),
b) Imazethapyr in the range of 1% to 30% (w/w),
c) emulsifiers in the range of 1% to 30% (w/w), and
d) solvents in the range of 1% to 80% (w/w).

In another embodiment, the present invention provides an emulsifiable concentrate composition comprising:
a) Fenoxaprop-P-ethyl in the range of 1% to 30% (w/w),
b) Imazethapyr in the range of 1% to 30% (w/w),
c) blend of anionic/nonionic surfactants in the range of 1% to 20% (w/w),
d) butyl polyalkylene oxide block copolymer in the range of 1% to 10% (w/w),
e) dimethyl sulfoxide in the range of 1% to 40% (w/w),
f) blend of N,N-dimethyl octan/ decanamide in the range of 1% to 20% (w/w), and
g) solvent naphtha (Petroleum), heavy aromatic the range of 1% to 30% (w/w).

In another embodiment, the present invention provides a soluble concentrates composition comprising:
a) Clodinafop-propargyl in the range of 1% to 30% (w/w),
b) Imazethapyr in the range of 1% to 30% (w/w),
c) emulsifiers in the range of 1% to 30% (w/w),
d) stabilizers in the range of 1% to 10% (w/w), and
e) solvents in the range of 1% to 80% (w/w).

In another embodiment, the present invention provides a soluble concentrates composition comprising:
a) Clodinafop-propargyl in the range of 1% to 30% (w/w),
b) Imazethapyr in the range of 1% to 30% (w/w),
c) blend of anionic/nonionic surfactants in the range of 1% to 20% (w/w),
d) butyl polyalkylene oxide block copolymer in the range of 1% to 10% (w/w),
e) ammonia solution 25% in the range of 1% to 10% (w/w),
f) propylene carbonate in the range of 1% to 20% (w/w),
g) blend of N,N-dimethyl octan/ decanamide in the range of 1% to 20% (w/w), and
h) distilled water in the range of 1% to 40% (w/w).

In another embodiment, the present invention provides process for preparation of a composition comprising the steps of:
a) weighing all the active ingredients,
b) mixing all the ingredients under stirring,
c) filtering the obtained material and packing.

In another embodiment, the present invention provides a process for preparation of emulsifiable concentrate composition comprising the steps of:
a) charging the dimethyl sulfoxide solvent under stirring followed by Fenoxaprop-P-ethyl and continue to stir for 15 minutes,
b) charging solvent naphtha (Petroleum) under continuous stirring and add Imazethapyr with continuous stirring for 30 mins,
c) charging blend of N,N-dimethyl octan/decanamide, blend of anionic/nonionic surfactants and butyl polyalkylene oxide block copolymer and stirring for 1 hour,
d) filtering the obtained material and packing.

In another embodiment, the present invention provides a process for preparation of soluble concentrates composition comprising the steps of:
a) charging the water solvent under stirring followed by Imazethapyr and continue to stir for 15 minutes,
b) adding N,N-dimethyl octan/ decanamide and propylene carbonate to the above mixture and stirring for 15 minutes,
c) adding clodinafop – propargyl to the above mixture and stirring for 15 minutes,
d) charging blend of anionic/nonionic surfactants and butyl polyalkylene oxide block copolymer and stirring for 1 hour,
e) filtering the obtained material and packing.

DETAILED 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.

The present invention provides synergistic composition comprising combination of 1 : 10 to 10 : 1 of first active ingredient to the second active ingredient, more preferably in the ratio of 1 : 5 to 5 : 1. However, variables of the ratios of each of the active ingredients can be used and the selection of the particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease 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.

The composition of the present invention could be applied to plants, seeds, fruits, soil as preventive and curative state.

ECs and SLs compositions are versatile formulations that can be applied with many types of sprayers. These composition enable spontaneous emulsification upon dilution and are easy to handle and measure. Very little agitation is required to mix them with water, and will not separate; Little visible residue on the plant; Do not wear sprayer parts or plug screens or nozzles; Seldom leaves visible residue

The emulsifier used in the composition allows the active ingredient in the solvent to mix with water, this form an emulsion. The emulsifying surfactant system enabling to form an oil-in-water emulsion when the formulation is added to water is typically a mixture of two or more surfactants, at least one of which is a nonionic surfactant and optionally at least one of which is an anionic surfactant.

The surfactants customarily employed in formulation technology, which are described, inter alia, in “Mc Cutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag, Munich Nienna, 1981 and M. and J. Ash, “Encyclopedia of Surfactants”, Vol I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for preparation of the herbicidal compositions according to the invention.

Anionic surfactants suitable for use in the invention may be any known in the art. The anionic surfactants may be polyarylphenol polyalkoxyether sulfates and/or phosphates; C8-18 alcohol polyalkoxyether phosphates, carboxylates, and/or citrates; alkyl benzenesulfonic acids; C8-20 alkyl carboxylates including fatty acids; C8-20 alcohol sulfates; C8-20 alcohol phosphate mono- and diesters; C8-20 alcohol and (C8-20alkyl)phenol polyoxyethylene ether carboxylates, sulfates and sulfonates; C8-20 alcohol and (C8-20 alkyl)phenol polyoxyethylene phosphate mono- and diesters; C8-20 alkylbenzene sulfonates (Geronol FF4 and Geronol FF6 etc), naphthalene sulfonates and formaldehyde condensates thereof; lignosulfonates; C8-20 alkyl sulfosuccinates and sulfosuccinamates; C8-20 acyl glutamates, sarcosinates, isethionates and taurates; water-soluble soaps and mixtures thereof.

Exemplary polyarylphenol polyalkoxyether sulfates and phosphates include polyarylphenol polyethoxyether sulfates and phosphates, polyarylphenol polypropoxyether sulfates and phosphates, polyarylphenol poly(ethoxy/propoxy)ether sulfates and phosphates, and salts thereof. The term “aryl” includes, for example, phenyl, tolyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, styryl, pyridyl, quinolinyl, and mixtures thereof. Exemplary polyarylphenol polyethoxyether sulfates and phosphates include distyrylphenol polyethoxyether sulfates and phosphates, and tristyrylphenol polyethoxyether sulfates and phosphates. The polyarylphenol polyalkoxether sulfates and phosphates may have a degree of alkoxylation (e.g., ethoxylation) of between about 1 and about 50, preferably between about 2 and about 40, more preferably between about 5 and about 30. Commercially available polyarylphenol polyalkoxyether sulfates and phosphates include, for example, SOPROPHOR® 4 D 384 (tristyrylphenol (EO)16 sulfate ammonium salt), SOPROPHOR® 3 D 33 (tristyrylphenol (EO)16 phosphate free acid), SOPROPHOR® FLK (tristyrylphenol (EO)16 phosphate potassium salt) and SOPROPHOR® RAM/384 (tristyrylphenol polyethoxylated ether sulfate neutralized with polyethoxylated oleylamine). In other embodiments, the polyarylphenol polyalkoxyether sulfates and phosphates may be mono-arylphenol polyalkoxyether sulfates and phosphates, such as styrylphenol polyethoxyether sulfates and phosphates.

Exemplary C8-18 alcohol polyethoxyether phosphates, carboxylates and citrates include STEPFAC® 8180 (tridecylalcohol (EO)3 phosphate), STEPFAC® 8181 (tridecylalcohol (EO)6 phosphate), STEPFAC® 8182 (tridecylalcohol (EO)12 phosphate), EMCOL® CN-6 (tridecylalcohol (EO)6 carboxylate). The C8-18 alcohol polyethoxyether phosphates, carboxylates and citrates may have a degree of ethoxylation of between about 1 and about 25, preferably between about 1 and about 20.

Exemplary alkylbenzene sulfonic acids and salts thereof include dodecylbenzene sulfonic acid, and metal (for example sodium or calcium, Atlox™ 4838B), ammonia or amine salts of the alkylbenzene sulfonic acids, including dodecylbenzene sulfonic acid. Amine neutralized versions include primary amines, diamines, triamines and alkanol amines.

Additional preferred anionic surfactants include (C8-12 alkyl)phenol polyoxyethylene ether sulfates, and (C8-12 alkyl)phenol polyoxyethylene phosphate mono- and diesters, accompanied in each case by monovalent counterions. In one embodiment the monovalent counterion for a (C8-12 alkyl)phenol polyoxyethylene ether sulfate or a (C8-12 alkyl)phenol polyoxyethylene phosphate is a protonated polyoxyethylene C12-20 alkylamine surfactant. More specifically, polyoxyethylene tallowamine salt of a nonylphenol polyoxyethylene ether sulfate, nonylphenol polyoxyethylene phosphate, and a blend of such nonylphenol polyoxyethylene phosphate with polyoxyethylene tallowamine.

The composition of the present invention may also include non-ionic surfactant as additional emulsifier, which is a water-soluble, 20 to 250 ethylene glycol ether groups containing butyl polyalkylene oxide block copolymer (Toximul 8320), ethylene diamino polypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl moiety, the substances normally contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples of non-ionic surfactants are nonylphenol polyethoxy ethanols, vegetable oil polyglycol ethers, polyadducts of ethylene oxide and propylene oxide, tributyl phenoxy polyethoxy ethanol (ethylan NS 500), octyl phenoxy polyethoxy ethanol.

The composition of the present invention may also include a blend of anionic and non-ionic surfactant as emulsifier, For example Unitop DVA-RES, Atlox 4853B etc.

The emulsifier is present in the composition in a range of about 1 to 30%, more preferably 2 to 20% of the total weight of the composition.

The composition of the present invention may also include additional stabiliser as used herein is also an emulsifier used herein above or epoxylates vegetable oils such as Epoxidized soybean oil (ESO), butylated hydroxytoluene (BHT), polyethyleneglycol or polypropyleneglycol chain or an ethylene glycol-propylene glycol copolymeric chain, or a mixture of these compounds, , polyoxyethylene-alkylethers, polyoxyethylene-alkylarylethers, polyoxypropylene-alkylethers, polyoxypropylene-alkylarylethers, polyoxyethylene-polyoxypropylene block polymers, aqueous ammonia, ammonium hydroxide etc.

The stabiliser is present in the composition in a range of about 1 to 10%, more preferably 1 to 5% of the total weight of the composition.

Solvent as used herein is a suitable water-immiscible solvents selected from the group consisting of water, aromatic hydrocarbons, aliphatic hydrocarbons, dialkylene glycol dialkyl ethers (diethylene glycol dimethyl ether), propylene carbonate, ketones, alkyl esters of acetic acid or mixtures thereo. Aromatic and aliphatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, mineral oil or kerosene or substituted naphthalenes, polar aprotic solvents such as DMSO, DMF, NMP etc, blend of N,N-dimethyl octan/ decanamide (Armid DM810), mixtures of mono- and polyalkylated aromatics are commercially available under the registered trademarks, Solvent C-IX, Solvesso® line solvent naphtha (Petroleum), heavy aromatic (Solvesso-200), and Shellsol® and Petrol Spezial®.

The solvents are present in the composition in a range of about 1 to 80%, more preferably 10 to 80% of the total weight of the composition.

Fenoxaprop-P-ethyl and Imazethapyr may be present in the composition or applied in any amounts relative to each other, to provide the enhanced or synergistic effect of the mixture. Fenoxaprop-P-ethyl and Imazethapyr may be present in the synergistic herbicidal composition in any suitable amount, and is generally present in an amount from 1% to 30% by weight of the composition, preferably from 1% to 20% by weight of the composition. However, variables of the ratios of each of the active ingredients can be used and the selection of the particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease 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.

Clodinafop-propargyl and Imazethapyr may be present in the composition or applied in any amounts relative to each other, to provide the enhanced or synergistic effect of the mixture. Clodinafop-propargyl and Imazethapyr may be present in the synergistic herbicidal composition in any suitable amount, and is generally present in an amount from 1% to 30% by weight of the composition, preferably from 1% to 20% by weight of the composition. However, variables of the ratios of each of the active ingredients can be used and the selection of the particular amount is dependent upon many factors including, for example, type of formulations, the crop, disease 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.

Formulation includes water soluble concentrate (SL), an emulstifiable concentrate (EC), an emulsion (EW), a microemulsion (ME), a suspension concentrates (SC), an oil-dispersions (OD), a flowable suspension (FS), water soluble powder (WS), water-dispersible granule (WDG), water-soluble granule (SG), a water-dispersible powder (WP), a water soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), an aqueous suspoemulsion (SE), capsule suspension (CS) and a microgranule (MG).

Preferably, the synergistic pesticidal composition can be formulated as Emulfiable concentrate (EC) or a soluble concentrate (SL).

The EC compositions of the present invention can be diluted with water or water solutions of agronomic compounds before use to produce a sprayable suspension composition which is used in treating plants or increasing plant growth, Dilution in water usually results in suspensions, emulsions, suspoemulsions or solutions of the agrochemical active ingredient at a concentration of at least 0.001 g/l.

The SL compositions of the present invention can be further diluted with water or water solutions of agronomic compounds before use to produce a sprayable suspension composition which is used in treating plants or increasing plant growth, Dilution in water usually results in suspensions, emulsions, suspoemulsions or solutions of the agrochemical active ingredient at a concentration of at least 0.001 g/l.

A particular mode of administering the compositions of the present invention is the administration to the aboveground parts of plants, in particular to the leaves thereof (leaf-application). The number of applications and the administered doses are chosen in accordance with the biological and climatic conditions of life of the causative agent. The antifungal compositions though, can also be applied to the soil and get into the plants through the root system (systemic activity), in case the locus of the plants is sprayed with a liquid composition.

When using the active compound combinations according to the invention, the application rate can be varied within a relatively wide range, depending on the kind of application. For the treatment of parts of plants, the active-compound combination application rates are generally between 0.1 and 10,000 g/ha, preferably between 100 and 2500 g/ha. For seed dressing, the active compound combination application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 20 g per kilogram of seed. For the treatment of the soil, the active-compound combination application rates are generally between 0.1 and 10.000 g ha preferably between 1 and 5000 g/ha.

The following examples describes the nature of the invention which are given only for the purpose of illustrating the present invention in more detail and are not limitative and relate to solutions.

EXAMPLES
Example 1: Composition of Fenoxaprop p-ethyl 9% + Imazethapyr 9% EC:
S. No. Ingredients/Raw Materials quantity (% w/w)
1. Fenoxaprop p-ethyl @ 96.20% (b) 9.0 % 9.35
2. Imazethapyr @98.2% (b) 9.0% 9.16
3. Dimethyl sulfoxide (DMSO) 30
4. blend of N,N-dimethyl octan/ decanamide (Armid DM810) 10
5. Blend of anionic/nonionic surfactants (Unitop DVA-RES) 5.0
6. Blend of anionic/nonionic surfactants (Atlox 4853B) 8.0
7. butyl polyalkylene oxide block copolymer (Toximul 8320) 2.0
8. Solvent naphtha (Petroleum), heavy aromatic (Solvesso-200) 26.49
Total 100

Manufacturing process:

DMSO solvent was charged to a clean reactor vessel under stirring according to the batch size, followed by Fenoxaprop-P-ethyl and continues to stir for 15 minutes. Solvesso 200 was charged under continuous stirring and Imazethapyr technical was charged to the above step and continue to stir for 30 mins. Armid DM810, Unitop DVA-RES, Atlox 4853B and Toximul 8320 were charged and the contents stirred for 1 hour. The mixture was passed through 10µ sieve filter paper and the material was collected and packed.

Example 2: Composition of Clodinafop - propargyl 9% + Imazethapyr 11 % SL:
S. No. Ingredients/Raw Materials quantity (% w/w)
1. Clodinafop propargyl @ 97.0% (b) 9.0 % 9.27
2. Imazethapyr @98.2% (b) 11.0% 11.20
3. Propylene carbonate 15.0
4. Blend of N,N-dimethyl octan/ decanamide (Armid DM 810) 15.53
5. Ammonia solution 25% 4.0
6. Blend of anionic/nonionic surfactants (Unitop DVA-RES) 5.0
7. Blend of anionic/nonionic surfactants (Atlox 4853B) 8.0
8. Butyl polyalkylene oxide block copolymer (Toximul 8320) 2.0
9. Distilled water 30.0
Total 100

Manufacturing process:

Water solvent was charged to a clean reactor vessel under stirring according to the batch size, followed by Imazethapyr technical and continue to stir for 15 minutes. Imazethapyr technical was slowly added under continuous stirring and the pH of the reaction mass adjusted to 7.5-8.0. Armid DM 810 and Propylene carbonate was charged to the above mass and continued stirring for 15 mins. clodinafop - propargyl technical was charged to the above step and continue to stir for 15 mins. Unitop DVA-RES, Atlox 4853B and Toximul 8320 were charged and the contents stirred for 1 hour. The mixture was passed through 10µ sieve filter paper and the material was collected and packed.

Field Efficacy Studies of Fenoxaprop p-ethyl and Imazethapyr

Soybean is an important rainy season crop of India. In India, it is grown on an area of 108.83 lakh ha with an annual production of 104.36 lakh million tonnes. Successful weed control is most important factor for fruitful soybean production because losses due weeds have been one of the major limiting factors in soybean production. Weeds compete with crop for light moisture and nutrients. Being a rainy season crop soybean faces severe weed competition during crop growth, resulting in a loss of about 40-60% of the potential yield. 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 Fenoxaprop p-ethyl and Imazethapyr. The active ingredient Imazethapyr in the combination, belongs to chemical family Imidazolinones with mode of action of “ALS inhibitors” (inhibition of acetolactate synthase) and Fenoxaprop-p-ethyl belongs to chemical family “Aryloxyphenoxypropionates” with mode of action of ACCase inhibitor (inhibition of Acetyl CoA Carboxylase). This combination helps in controlling the cross-spectrum weeds (broad leaf weeds, grassy weeds and sedges) in soybean when applied in early post-emergence (18-22 DAS or 2-3 weed leaf stage) application timing. Both the molecules are safe to soybean.

The weed control activity of the individual herbicides of the invention and their combinations were evaluated on weeds such as Acalypha indica, Anotis montena, Commelina communis, Digera arvensis, Echinochloa colona and Dinebra retroflexa. Trials were conducted with randomized block design with net plot size of 5m x 6m. Each trial was replicated four times and conducted under GEP guidelines. Spraying was done with manual operated backpack knapsack sprayer with 300 L of water spray volume per hectare at early post-emergence (18-22 DAS or 2-3 weed leaf stage) 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 15 days after application. These observations are to be taken from entire plot. The herbicide tank mix combinations, application rates, plant species tested, and results are given in the following tables:

Table 1: Table 1 demonstrates synergy on weeds using the combination of Fenoxaprop p-ethyl and Imazethapyr. The field trials were carried out in India at various locations. The percentage efficacy was calculated after 15 days of application. The target weeds were Anotis montena and Commelina communis and the results are recorded in the table 1 below:

Active Dose (GAH) % Weed Control of Anotis montena % Weed Control of Commelina communis
Fenoxaprop p-ethyl EC 112.5 0 0
Imazethapyr SL 112.5 80 70
Fenoxaprop p-ethyl + Imazethapyr EC (Example 1) 112.5 + 112.5
90
80

The results in table 1 clearly demonstrates synergy between Fenoxaprop p-ethyl and Imazethapyr against weeds like, Anotis montena and Commelina communis.

Table 2: Table 2 demonstrates synergy on weeds using the combination of Fenoxaprop p-ethyl and Imazethapyr. The field trials were carried out in India at various locations. The percentage efficacy was calculated after 15 days of application. The target weeds were Echinochloa colonum and Dinebra retroflexa and the results are recorded in the table 2 below:

Active Dose (GAH) % Weed Control of Echinochloa colonum % Weed Control of Dinebra retroflexa
Fenoxaprop p-ethyl EC 112.5 90 90
Imazethapyr SL 112.5 30 70
Fenoxaprop p-ethyl + Imazethapyr EC (Example 1) 112.5 + 112.5
95
100

The results in table 2 clearly demonstrates efficacy of Fenoxaprop p-ethyl and Imazethapyr against weeds like Echinochloa colonum and Dinebra retroflexa.

Table 3: Table 3 demonstrates synergy on weeds using the combination of Fenoxaprop p-ethyl and Imazethapyr. The field trials were carried out in India at various locations. The percentage efficacy was calculated after 15 days of application. The target weeds were Acalypha indica and Digera arvensis and the results are recorded in the table 3 below:

Active Dose (GAH) % Weed Control of Acalypha indica % Weed Control of Digera arvensis
Fenoxaprop p-ethyl EC 112.5 0 0
Imazethapyr SL 112.5 70 90
Fenoxaprop p-ethyl + Imazethapyr EC (Example 1) 112.5 + 112.5
75
95

The results in table 3 clearly demonstrates efficacy of Fenoxaprop p-ethyl and Imazethapyr against weeds like, Acalypha indica and Digera arvensis.

Field Efficacy Studies of Clodinafop and Imazethapyr
Soybean is an important rainy season crop of India. In India, it is grown on an area of 108.83 lakh ha with an annual production of 104.36 lakh million tonnes. Successful weed control is most important factor for fruitful soybean production because losses due weeds have been one of the major limiting factors in soybean production. Weeds compete with crop for light moisture and nutrients. Being a rainy season crop soybean faces severe weed competition during crop growth, resulting in a loss of about 40-60% of the potential yield. 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 Clodinafop and Imazethapyr. The active ingredient Imazethapyr in the combination, belongs to chemical family Imidazolinones with mode of action of “ALS inhibitors” (inhibition of acetolactate synthase) and Clodinafop belongs to chemical family “Aryloxyphenoxypropionates” with mode of action of ACCase inhibitor (inhibition of Acetyl CoA Carboxylase). This combination helps in controlling the cross-spectrum weeds (broad leaf weeds, grassy weeds and sedges) in soybean when applied in early post-emergence (18-22 DAS or 2-3 weed leaf stage) application timing. Both the molecules are safe to soybean.

The weed control activity of the individual herbicides of the invention and their combinations were evaluated on weeds such as Acalypha indica, Anotis montena, Commelina communis, Digera arvensis, Echinochloa colona and Dinebra retroflexa. Trials were conducted with randomized block design with net plot size of 5m x 6m. Each trial was replicated four times and conducted under GEP guidelines. Spraying was done with manual operated backpack knapsack sprayer with 300 L of water spray volume per hectare at early post-emergence (18-22 DAS or 2-3 weed leaf stage) 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 15 days after application. These observations are to be taken from entire plot. The herbicide tank mix combinations, application rates, plant species tested, and results are given in the following tables:

Table 4: Table 4 demonstrates synergy on weeds using the combination of Clodinafop and Imazethapyr. The field trials were carried out in India at various locations. The percentage efficacy was calculated after 15 days of application. The target weeds were Anotis montena and Commelina communis and the results are recorded in the table 4 below:

Active Dose (GAH) % Weed Control of Anotis montena % Weed Control of Commelina communis
Clodinafop WP 100 0 0
Imazethapyr SL 100 80 70
Clodinafop + Imazethapyr SL (Example 2) 100 + 100
90
75

The result in table 4 clearly demonstrates synergy between Clodinafop and Imazethapyr against weeds like, Anotis montena and Commelina communis.

Table 5: Table 5 demonstrates synergy on weeds using the combination of Clodinafop and Imazethapyr. The field trials were carried out in India at various locations. The percentage efficacy was calculated after 15 days of application. The target weeds were Echinochloa colonum and Dinebra retroflexa and the results are recorded in the table 5 below:

Active Dose (GAH) % Weed Control of Echinochloa colonum % Weed Control of Dinebra retroflexa
Clodinafop WP 100 90 85
Imazethapyr SL 100 20 70
Clodinafop + Imazethapyr SL (Example 2) 100 + 100
95
96

The results in table 5 clearly demonstrates efficacy of Clodinafop and Imazethapyr against weeds like Echinochloa colonum and Dinebra retroflexa.

Table 6: Table 6 demonstrates synergy on weeds using the combination of Clodinafop and Imazethapyr. The field trials were carried out in India at various locations. The percentage efficacy was calculated after 15 days of application. The target weeds were Acalypha indica and Digera arvensis and the results are recorded in the table 6 below:

Active Dose (GAH) % Weed Control of Acalypha indica % Weed Control of Digera arvensis
Clodinafop WP 100 0 0
Imazethapyr SL 100 70 95
Clodinafop + Imazethapyr SL (Example 2) 100 + 100
75
100

The results in table 6 clearly demonstrates efficacy of Clodinafop and Imazethapyr against weeds like, Acalypha indica and Digera arvensis.

,CLAIMS:
WE CLAIM:
1. A synergistic herbicidal composition comprising:
a) phenoxy herbicide selected from Fenoxaprop-P-ethyl and Clodinafop-propargyl,
b) Imazethapyr,
c) emulsifiers, and
d) other agrochemical auxiliaries.

2. The composition as claimed in claim 1, wherein said composition is in the form of Emulsifiable concentrate (EC) or Soluble concentrates (SL).

3. The composition as claimed in claim 1, wherein said emulsifiers are selected from blend of anionic/nonionic surfactants and butyl polyalkylene oxide block copolymer or combinations thereof.

4. The composition as claimed in claim 1, wherein said other agrochemical auxiliaries are selected from stabiliser and solvents.

5. The composition as claimed in claim 1, wherein said stabilisers selected from epoxylates vegetable oils such as Epoxidized soybean oil (ESO), butylated hydroxytoluene (BHT), polyethyleneglycol or polypropyleneglycol chain or an ethylene glycol-propylene glycol copolymeric chain, aqueous ammonia and ammonium hydroxide or mixtures thereof.

6. The composition as claimed in claim 1, wherein said solvents are selected from water, aromatic hydrocarbons, aliphatic hydrocarbons, dialkylene glycol dialkyl ethers, propylene carbonate, ketones, alkyl esters of acetic acid, aromatic and aliphatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, mineral oil or kerosene or substituted naphthalenes, polar aprotic solvents such as DMSO, DMF, NMP etc, blend of N,N-dimethyl octan/ decanamide, mixtures of mono- and polyalkylated aromatics, solvent C-IX, solvent naphtha (Petroleum), heavy aromatic.

7. The composition as claimed in claims 1 to 6, wherein said emulsifiable concentrate composition comprising:
a) Fenoxaprop-P-ethyl in the range of 1% to 30% (w/w),
b) Imazethapyr in the range of 1% to 30% (w/w),
c) blend of anionic/nonionic surfactants in the range of 1% to 20% (w/w),
d) butyl polyalkylene oxide block copolymer in the range of 1% to 10% (w/w),
e) dimethyl sulfoxide in the range of 1% to 40% (w/w),
f) blend of N,N-dimethyl octan/ decanamide in the range of 1% to 20% (w/w), and
g) solvent naphtha (Petroleum), heavy aromatic the range of 1% to 30% (w/w).

8. The composition as claimed in claims 1 to 6, wherein said soluble concentrates composition comprising:
a) Clodinafop-propargyl in the range of 1% to 30% (w/w),
b) Imazethapyr in the range of 1% to 30% (w/w),
c) blend of anionic/nonionic surfactants in the range of 1% to 20% (w/w),
d) butyl polyalkylene oxide block copolymer in the range of 1% to 10% (w/w),
e) ammonia solution 25% in the range of 1% to 10% (w/w),
f) propylene carbonate in the range of 1% to 20% (w/w),
g) blend of N,N-dimethyl octan/ decanamide in the range of 1% to 20% (w/w), and
h) distilled water in the range of 1% to 40% (w/w).

9. The process for the preparation of emulsifiable concentrate composition as claimed in claim 7, wherein said process comprising the steps of:
a) charging the dimethyl sulfoxide solvent under stirring followed by Fenoxaprop-P-ethyl and continue to stir for 15 minutes,
b) charging solvent naphtha (Petroleum) under continuous stirring and add Imazethapyr with continuous stirring for 30 mins,
c) charging blend of N,N-dimethyl octan/ Decanamide, blend of anionic/nonionic surfactants and butyl polyalkylene oxide block copolymer and stirring for 1 hour,
d) filtering the obtained material and packing.

10. The process for the preparation of emulsifiable concentrate composition as claimed in claim 8, wherein said process comprising the steps of:
a) charging the water solvent under stirring followed by Imazethapyr and continue to stir for 15 minutes,
b) adding N,N-dimethyl octan/decanamide and Propylene carbonate to the above mixture and stirring for 15 minutes,
c) adding clodinafop–propargyl to the above mixture and stirring for 15 minutes,
d) charging blend of anionic/nonionic surfactants and butyl polyalkylene oxide block copolymer and stirring for 1 hour,
e) filtering the obtained material and packing.

Dated this Twenty Seventh (27th) day of August, 2021

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