DESC:FORM 2

THE PATENTS ACT 1970
(SECTION 39 OF 1970)

&

THE PATENT RULES, 2003

COMPLETE SPECIFICATION
(Section 10 and Rule 13)

EMULSIFIABLE CONCENTRATE COMPOSITIONS OF QUIZALOFOP-ETHYL AND PROCESS FOR PREPARING 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 Emulsifiable Concentrate (EC) compositions of a herbicide.

The present invention specifically relates to Emulsifiable Concentrate (EC) compositions of Quizalofop or its salts or its ester.

The present invention specifically relates to Emulsifiable Concentrate (EC) compositions of Quizalofop-ethyl and other agrochemical auxiliaries.

The present invention specifically relates to Emulsifiable Concentrate (EC) compositions of Quizalofop-ethyl, comprising one or more emulsifiers, adjuvants and filler.

The present invention also relates to a process for the preparation of Emulsifiable Concentrate (EC) compositions of Quizalofop-ethyl, comprising one or more emulsifiers, adjuvants and filler by mixing all the ingredients under stirring and homogenizing the resultant mixture.

BACKGROUND OF THE INVENTION
Quizalofop-ethyl is a chemical compound from the group of aryloxyphenoxypropionic-herbicides (a sub-group of derivatives of phenoxyacetic acid and of quinoxaline). Quizalofop-ethyl is a representative of Quizalofop herbicides, structurally the ethyl ester of Quizalofop, and the free acid. Chemically Quizalofop-ethyl is known as (RS)-2-[4-(6-chlorchinoxalin-2-yloxy)phenoxy]propionic acid ethyl ester.

Quizalofop is a selective post-emergence herbicide. Quizalofop appears as two different isomer mixtures: Quizalofop-ethyl and Quizalofop-p-ethyl. Quizalofop-p-ethyl is composed solely of the pesticidally active isomer, and all Quizalofop products currently in the marketplace contain this isomer; there are no pesticide registrations for products containing Quizalofop-ethyl (a 50/50 racemic mixture of active and inactive isomers). Both Quizalofop-p-ethyl and Quizalofop-ethyl are referred to collectively as Quizalofop. The chemical name of Quizalofop-p-ethyl is (R)-2-[4-(6-Chlorchinoxalin-2-yloxy)phenoxy]propionic acid ethyl ester and the structure of Quizalofop-p-ethyl is as given below:

Quizalofop-p-ethyl is a selective, post-emergence organic phenoxy herbicide that belongs to a subclass of phenoxy compounds known as Aryloxyphenoxys (fops). Quizalofop-p-ethyl is absorbed by the treated foliage and translocated to the roots and other growing points of the plant.

Quizalofop is a systemic herbicide registered for use to control annual and perennial weeds in various food/feed and non-food/non-feed crops. Quizalofop-ethyl is a 50/50 racemic mixture of R- and S-enantiomers. Quizalofop-p-ethyl is the purified R-enantiomer. The pesticidally active isomer is the R-enantiomer (Quizalofop-p-ethyl).

ECs are versatile formulations that can be applied with many types of sprayers. EC compositions enable spontaneous emulsification upon dilution and are easy to handle and measure.

Quizalofop ethyl 5% EC as formulation, Quizalofop ethyl 10% EC, 15% EC and 20% EC are currently available. However, the information of compositions and specific ingredients used in these products is not available in the market.

US 6,878,674 B2 discloses a pesticidal emulsifiable concentrate composition consisting of a phenoxypropionate herbicide, a polar solvent, a non-polar solvent and a surfactant, wherein said polar solvent is N-methyl-2-pyrrolidone.

The inventors of the present invention have surprisingly found Quizalofop-P-Ethyl EC formulations containing specific proprietary emulsifier and adjuvants which is stable over shelf life and is easily mixable, provide spontaneous emulsification upon dilution.

OBJECTIVE OF THE INVENTION
The main objective of the present invention is to provide Emulsifiable Concentrate (EC) compositions of a herbicide.

Another objective of the present invention is to provide Emulsifiable Concentrate (EC) compositions of Quizalofop or its salts or its ester.

Yet another objective of the present invention is to provide Emulsifiable Concentrate (EC) compositions of Quizalofop-ethyl and other agrochemical auxiliaries.

Still another objective of the present invention is to provide Emulsifiable Concentrate (EC) compositions of Quizalofop-ethyl, comprising one or more emulsifiers, adjuvants and filler.

Still another objective of the present invention is to provide to a process for the preparation of Emulsifiable Concentrate (EC) compositions of Quizalofop-ethyl, comprising one or more emulsifiers, adjuvants and filler by mixing all the ingredients under stirring and homogenizing the resultant mixture.

In yet another objective of the present invention is to provide Emulsifiable Concentrate (EC) compositions of Quizalofop-ethyl as herbicide for application to plants.

SUMMARY OF THE INVENTION
Accordingly, the present invention provides an emulsifiable concentrate compositions of a herbicide.

One embodiment of the present invention provides an emulsifiable concentrate compositions of Quizalofop or its salts or its ester.

Another embodiment of the present invention provides an emulsifiable concentrate compositions of Quizalofop-ethyl and other agrochemical auxiliaries.

Yet another embodiment of the present invention provides an emulsifiable concentrate compositions of Quizalofop-ethyl, comprising one or more emulsifiers, adjuvant and filler.

Yet another embodiment of the present invention provides emulsifiable concentrate compositions comprising:
(a) Quizalofop-ethyl,
(b) blend of anionic & nonionic surfactants in aromatic hydrocarbon,
(c) polyether modified trisiloxane, and
(d) solvent.

Yet another embodiment of the present invention provides an emulsifiable concentrate compositions comprising:
(a) Quizalofop-ethyl in the range of 4% to 10% (w/w),
(b) blend of anionic & nonionic surfactants in aromatic hydrocarbon in the range of 5% to 20% (w/w),
(c) polyether modified trisiloxane in the range of 1% to 3%(w/w), and
(d) solvent in the range of 20% to 90% (w/w).

Yet another embodiment of the present invention provides an emulsifiable concentrate compositions comprising:
(a) Quizalofop-ethyl in the range of 4% to 10% (w/w),
(b) blend of (x)-sorbitan mono-9-octadecenoate poly(oxy-1,2-ethanediyl) poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 ylbenzenesulfonate in the range of 3% to 10% (w/w),
(c) poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 yl benzenesulfonate in the range of 2% to 10% (w/w),
(d) polyether modified trisiloxane in the range of 1% to 3% (w/w), and
(e) aromatic hydrocarbon solvent in the range of 20% to 90% (w/w).

Still another embodiment of the present invention provides a process for the preparation of emulsifiable concentrate compositions of Quizalofop-ethyl, comprising one or more emulsifiers, adjuvant and filler by mixing all the ingredients under stirring and homogenizing the resultant mixture.

Yet another embodiment of the present invention provides a process for the preparation of emulsifiable concentrate compositions comprising steps of:
(a) adding Quizalofop-ethyl technical to aromatic hydrocarbon solvent under stirring,
(b) adding polyether modified trisiloxane slowly under stirring,
(c) adding blend of anionic & nonionic surfactants under stirring and homogenizing sample and
(d) packing the composition in suitable container.

Yet another embodiment of the present invention provides a process for the preparation of emulsifiable concentrate compositions comprising steps of:
(a) adding Quizalofop-ethyl technical to aromatic hydrocarbon solvent under stirring,
(b) adding polyether modified trisiloxane slowly under stirring,
(c) adding blend of (x)-sorbitan mono-9-octadecenoate poly(oxy-1,2-ethanediyl) poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 ylbenzenesulfonate and poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 yl benzenesulfonate under stirring and homogenizing sample and
(d) packing the composition in suitable container.

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

In preferred embodiment the Quizalofop-ethyl EC composition comprises from
- 4% to 10% (w/w) of Quizalofop-ethyl as active ingredient,
- 5% to 20% (w/w) of emulsifier, and
- 0.1% to 90% (w/w) of other additives / solvent / auxiliaries.

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 the EC 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.
Preferably blend of anionic & nonionic surfactants in aromatic hydrocarbon.

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 (C8-20 alkyl)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® 4D384 (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.

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 polyadducts of ethylene oxide and propylene oxide (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 preferably includes a blend of anionic and non-ionic surfactant as emulsifier. For example Unitox-33, Unitox-65, Unitop DVA-RES, Atlox 4853B etc.

More preferably, the emulsifier is a blend of (x)-Sorbitan mono-9-octadecenoate
poly(oxy-1,2-ethanediyl), poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 ylbenzenesulfonate (Unitox-33) and / or poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 ylbenzenesulfonate (Unitox-65).

The emulsifier is present in the composition in a range of about 1 to 30% (w/w), more preferably 5 to 20% (w/w) of the total weight of the composition.

The composition of the present invention additionally contains an adjuvant, as used herein is selected from and not limited to absorbed Polydimethyl siloxane, stearates; silicones (Sag-1572, SILFOAM®, SILFAR®, PULPSIL® and WACKER®) and ethoxylates. Preferably, the adjuvant is WACKER LO90.

The adjuvant is present in the composition in a range of about 1% to 5% (w/w), more preferably 1% to 3% (w/w)of the total weight of the composition.

Solvent as used herein is a suitable water-immiscible solvents selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, dialkylene glycol dialkyl ethers (diethylene glycol dimethyl ether), ketones, alkyl esters of acetic acid or mixtures thereto. 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® and Shellsol® and Petrol Spezial®.

The solvent is present in the composition in a range of about 10% to 90% w/w, more preferably 20% to 90% w/w% of the total weight of the composition.

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 EC compositions of the present invention can be used to control grass weeds in broad leaf crops like sugar beet, oilseed rape, sunflower, potatoes, vegetables, pineapple, soybean, field beans and other agricultural crops.

The present invention is further illustrated by the following examples which are provided merely to be exemplary of the inventions and is not intended to limit the scope of the invention. Certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the present invention.

EXAMPLES
Example-1:
Sr.No. Compositions %W/W Quantity in gm
1 Quizalofop -p- ethyl@97.1% (b) 5.2 5.35 53.5
2 Blend of (x)-sorbitan mono-9-octadecenoate
poly(oxy-1,2-ethanediyl) poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 yl benzenesulfonate (Unitox-33) (ADV) 6.0 55
3 Poly(oxy-1,2-ethanediyl), alpha-(tris(1-
phenylethyl)phenyl)-omega-hydroxy-
calcium, 4-dodecan-3 ylbenzenesulfonate (Unitox-65) 4.0 45
4 Polyether modified trisiloxane (WACKER LO 99) 1.5 15
5 Solvent C-IX 83.15 831.5
Total 100.0 1000

The composition of the present invention is prepared by a process which comprises:

Solvent C-IX was added to a clean vessel in accordance to the batch size and stirred at 500 rpm. To this appropriate quantity of Quizalofop-ethyl technical was added add slowly under stirring, followed by the adjuvant polyether modified trisiloxane according to the batch size. After stirring for 15 minutes the blend of (x)-sorbitan mono-9-octadecenoate poly(oxy-1,2-ethanediyl) poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 yl benzenesulfonate was add slowly under stirring followed by poly(oxy-1,2-ethanediyl), alpha-(tris(1- phenylethyl)phenyl)-omega-hydroxy- calcium, 4-dodecan-3 ylbenzenesulfonate and the mixture was homogenized for 60 min in a homogenizer. The obtained mixture was filtered and packed the material in the designated containers.

Field Efficacy trials

The field studies were conducted to compare the weed controlling activity of present invention- Quizalofop EC Vs marketed Quizalofop EC. This product helps in controlling the grassy weeds in soybean when applied in early post-emergence (18-22 DAS or 2-3 weed leaf stage) application timing.

The weed control activity of the individual treatments was evaluated on weeds such as Echinochloa colona and Dinebra retroflexa. Trials were conducted in Madhya Pradesh and Maharashtra. The trials were laid out with randomized block design keeping the 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 500 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 treatment’s, application rates, weed species tested, and results are given in the below table:

Table 1: Comparison of Quizalofop EC composition of present invention vs marketed Quizalofop EC composition against grassy weed in Soybean in Madhya Pradesh

Active
Dose (GAH) % Weed Control of Echinochloa colona % Weed Control of Dinebra retroflexa
Observed Observed
Quizalofop 5% EC Composition of present invention 50 92 95
marketed Quizalofop 5% EC composition 50 88 90
Observed % weed control difference 4 5

Table 2: Comparison of Quizalofop EC composition of present invention vs marketed Quizalofop EC composition against grassy weed in Soybean in Maharashtra

Active
Dose (GAH) % Weed Control of Echinochloa colona % Weed Control of Dinebra retroflexa
Observed Observed
Quizalofop 5% EC Composition of present invention 50 92 96
marketed Quizalofop 5% EC composition 50 90 92
Observed % weed control difference 2 4

The results presented in Tables 1 & 2 demonstrates the weed control of Quizalofop 5% EC composition of present invention was better as compared to marketed Quizalofop 5% EC compositions against weeds like Echinochloa colona and Dinebra retroflexa in Soybean. ,CLAIMS:WE CLAIM:
1. An emulsifiable concentrate compositions comprising:
(a) Quizalofop-ethyl in the range of 4% to 10% (w/w),
(b) blend of anionic & nonionic surfactants in aromatic hydrocarbon in the range of 5% to 20% (w/w),
(c) polyether modified trisiloxane in the range of 1% to 3% (w/w), and
(d) solvent in the range of 20% to 90% (w/w).
2. The composition as claimed in claim 1, wherein the blend of anionic & nonionic surfactants is blend of (x)-sorbitan mono-9-octadecenoate poly(oxy-1,2-ethanediyl) poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 ylbenzenesulfonate, poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 yl benzenesulfonate.
3. The composition as claimed in claim 1, wherein the solvent is aromatic hydrocarbons, aliphatic hydrocarbons, dialkylene glycol dialkyl ethers (diethylene glycol dimethyl ether), ketones, alkyl esters of acetic acid, aromatic and aliphatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, mineral oil, kerosene, substituted naphthalenes, polar aprotic solvents such as DMSO, DMF, NMP, blend of N,N-dimethyl octan/ decanamide, mixtures of mono and polyalkylated aromatics.
4. The composition as claimed in claims 1-3, wherein emulsifiable concentrate compositions comprising:
(a) Quizalofop-ethyl in the range of 4% to 10% (w/w),
(b) blend of (x)-sorbitan mono-9-octadecenoate poly(oxy-1,2-ethanediyl) poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 ylbenzenesulfonate in the range of 3% to 10% (w/w),
(c) poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 yl benzenesulfonate in the range of 2% to 10% (w/w),
(d) polyether modified trisiloxane in the range of 1% to 3%, and
(e) aromatic hydrocarbon solvent in the range of 20% to 90%.

5. The process for the preparation of emulsifiable concentrate composition as claimed in claim 1, wherein the process comprising steps of:
(a) adding Quizalofop-ethyl technical to aromatic hydrocarbon solvent under stirring,
(b) adding polyether modified trisiloxane slowly under stirring,
(c) adding blend of anionic & nonionic surfactants under stirring and homogenizing sample and
(d) packing the composition in suitable container.
6. The process for the preparation of emulsifiable concentrate composition as claimed in claim 4, wherein the process comprising steps of:
(a) adding Quizalofop-ethyl technical to aromatic hydrocarbon solvent under stirring,
(b) adding polyether modified trisiloxane slowly under stirring,
(c) adding blend of (x)-sorbitan mono-9-octadecenoate poly(oxy-1,2-ethanediyl) poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 ylbenzenesulfonate and poly(oxy-1,2-ethanediyl), alpha-(tris(1-phenylethyl)phenyl)-omega-hydroxy-calcium, 4-dodecan-3 yl benzenesulfonate under stirring and homogenizing sample and
(d) packing the composition in suitable container.

Dated this Twenty Second (22nd) day of March, 2022

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