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Synergistic Agrochemcial Composition With Insecticde For Reducing Phytotoxicity In Crops Treated With Herbicide

Abstract: A synergistic agrochemical composition comprising herbicide or mixture thereof; and an insecticide as a safener for reducing phytotoxicity in crops on post herbicide application and combination thereof. More particularly, the present invention relates to a agrochemical composition comprising bioactive amounts of (A) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grassy weeds or mixture thereof; (B) a one or more herbicide(s) selected from the group of various class of compounds for control of broad-leaved weeds and grassy weeds and sedges in economical crops or mixture thereof; and (C) an insecticide selected from the class of diamide, metadiamide or isoxazoline or mixture thereof for reducing phytotoxicity in crops on post herbicide application. The present invention further relates to process for preparing the said compositions in specific ratio. The present invention further relates to the process for preparing the said composition along with at least one inactive excipient; and formulations thereof. The present invention further relates to the synergistic agrochemical composition and to reduce phytotoxicity in crops on post herbicide application, wherein active ingredient present in fixed ratio shows synergy in a herbicidal activity.

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Patent Information

Application #
Filing Date
02 September 2020
Publication Number
09/2022
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
patent@infinventip.com
Parent Application
Patent Number
Legal Status
Grant Date
2024-02-07
Renewal Date

Applicants

RAJDHANI PETROCHEMICALS
Phase-1, Industrial Growth Center, SIDCO, Samba-184121, Jammu and Kashmir, India

Inventors

1. SHAH, Kenal V.
Phase-1, Industrial Growth Center, SIDCO, Samba-184121, Jammu and Kashmir, India
2. SHAH, Bhavesh V.
Phase-1, Industrial Growth Center, SIDCO, Samba-184121, Jammu and Kashmir, India
3. PATEL Dipakkumar
Phase-1, Industrial Growth Center, SIDCO, Samba-184121, Jammu and Kashmir, India

Specification

The present invention relates to synergistic agrochemical composition comprising herbicide(s) and mixture thereof; and Insecticide as a safener for reducing phytotoxicity in crops on post herbicide application. More particularly, the present invention relates to a herbicidal composition for weeds control in post emergence conditions comprising bioactive amounts of (A) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grassy weeds or mixture thereof; (B) a one or more herbicide(s) selected from the group of various class of compounds for control of broad-leaved weeds and grassy weeds and sedges in economical crops or mixture thereof; and (C) an insecticide selected from the class of diamide, metadiamide or isoxazoline or mixture thereof for reducing phytotoxicity in crops on post herbicide application. The present invention further relates to process of preparing said composition along with at least one inactive excipients and formulation thereof.

BACKGROUND OF THE INVENTION:
Weeds are a nuisance in most agricultural crops, orchards, plantation crops, landscapes and sometimes the herbicides used to control the weeds end up injuring crops, useful plants, some of ornamental plants. Herbicides are pesticides useful for killing or controlling unwanted plants. Generally, there are two kinds of herbicides- selective and non-selective. Selective herbicides kill certain target weeds while leaving the desired crop relatively unharmed while non-selective herbicides kill both the weeds and crops. Profitable crop production depends on effective weed control. The weeds can reduce field crop yields by competing for water, sunlight and nutrients. In today’s crop production systems, starting off with a good burn-down program is a must as it helps to achieve maximum initial crop growth and reduce weed interference during early stages of the crop cycle. Since the weed-crop competition is critical during the early stages of crop cycle, the weed interference at early stage has a direct impact on the yield of the crop.
Herbicide injury is observed after application of herbicide in terms of stunting, yellowing, scorching, epinasty, hyponasty, germination loss, poor plant population stand in field and even loss of crop or plant yield. It normally happens while not following the directions on the label as carefully as one should. Farmers tend to use more herbicide than the label instructs or can be careless and spray during windy conditions or wave the wand around so that the spray drifts onto non-target plants.
The term for plant damage is “phytotoxicity” and it can be caused by pesticides,
nutrients, or physical and environmental damage (wind, sun, hail, etc.). Often the
identity of the herbicide can be determined by the injury symptoms on the plants.
Symptoms can be divided into 5 main categories: leaf and shoot malformations,
root and shoot stunting, leaf spotting, leaf chlorosis (yellowing), and leaf necrosis
(death).
An effective weed control can be achieved by usage of herbicides appropriately. The activity of herbicides can be enhanced in various ways to achieve the maximum benefit. One of the ways is to use combinations. However, identifying appropriate combinations, which will reduce the toxicity at the same time due to the application of herbicides on crop, their agrochemical application rates and ratio of the combinations is essential to achieve efficacious control, which is not straight forward. The selection of a particular formulation type is more cumbersome for an agrochemical combination.
The efficacy of these herbicides against harmful weeds in the crop plants depends on the application rate, the formulation ingredients, the harmful weeds to be controlled, the climatic conditions and the soil conditions.
Farmers are applying more than one active ingredients or applying high use rate to control different types of weeds at a time, to control multiple generations of weeds in fields, to control troublesome weeds and to get residual control. Such practices increases the chances of herbicidal injury or phytotoxicity to the target crops.
There are many herbicides which used in combination creates characteristic phytotoxic injuries in plants like malformed, distorted leaves and shoots, stunted shoots and roots, chlorotic, necrotic, or spotted leaves.
However, there remains a great need for improved broadleaf and grassy weed control compositions and a method of controlling such noxious vegetation in pre and post emergence without adversely affecting desirable plants and which reduces the amount of chemical herbicidal agent necessary to obtain the acceptable weed control along with reducing the undesirable post treatment toxic effect or injury of the herbicides on crops.
The compound 2-[(2-chlorophenyl) methyl]-4,4-dimethyl-3-isoxazolidinone, also known as "clomazone", is a potent herbicide as evidenced by its ability to control, for full growing seasons and at low application rates. However, clomazone is phytotoxic to other crops when applied at rates effective to control undesired vegetation, such contact resulting from drift to adjacent fields planted with low tolerance crops or from carryover when soybean fields treated with clomazone are rotated to a crop sensitive to clomazone.
It has been known that certain insecticides act as a safener against injury inflicted by herbicide application. Article titled“Evaluation of Safening Effects to Herbicides Conferred via Insecticide Seed Treatments in Soybean (Glycine max) and Grain Sorghum (Sorghum bicolor)” by Nicholas Robert Steppig discloses that applications of some organophosphate insecticides at planting can reduce cotton injury following applications of the soil-applied herbicide clomazone.
There are many combinations of herbicides known in the art for the control of weeds further comprising an insecticides used as a safener. For example, WO 1989006492 A1 discloses a method of controlling undesirable vegetation at locus by applying to the locus clomazone and, as an antidote to clomazone, a safening amount of at least one organophosphorus compound.
EP2836072B1 relates to an herbicidal composition comprising a uracil compound as an active ingredient. Furthermore, the invention relates to methods of applying said mixture. The patent further relates to the herbiciedes like metamifop, Pinoxaden present in the composition.
US8802597B2 relates to certain pyrimidines group of herbicides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use for controlling undesirable vegetation. More precisely, the herbicidal composition comprising compounds like Propaquizafop, Bispyribac sodium, Chlorimuron ethyl along with more herbicidal compounds.
US8846571B2 relates to herbicidal compositions containing as active ingredients (a) a herbicidal benzoylpyrazole compound or its salt and (b) other herbicidal compound. The patent further relates to herbicidal mixture comprisies of herbicidal compounds like Chlorimuron ethyl, metribuzin, propargyl, pyroxasulfone.
There is however a need for improvement of these combinations. Further there is a need of a safener in the herbicidal composition which will reduce the unwanted phytotoxic effect on crops treated with the herbicides. An insecticide play a significant role in development of crop and reduces the phytotoxic effect. Single active combinations used over a long period of time has resulted in resistance. With the onset of resistance to certain weeds, there is a need in the art for a combination of actives that decreases chances of resistance and improves the spectrum of controlling grassy, broad leaf weeds and sedges with pre-emergence and post-emergence application.
Even though use of insecticide as safener to herbicide is known, the present invention provides an alternative composition for safening crops to the phytotoxic effects of herbicides in agriculture which will act as useful agronomic tool to farmers.
However still there is a need of herbicidal composition comprises of a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grasses or mixture thereof; a one or more herbicide(s) selected from the group of various class of compounds for control of broad-leaved weeds and grasses in crops of useful plants or mixture thereof; and an insecticide selected from the class of diamide, metadiamide or isoxazoline as safener for reducing phytotoxicity in crops treated with a herbicide or mixture thereof which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process.
In general use, the herbicidal actives are used in the form of a dilute aqueous composition because it can attain a good interaction with the target weed. However, most active herbicidal compounds that are used as pesticides are only sparingly or even insoluble in water. The low solubility of such compounds present the challenges and difficulties to formulator in formulating herbicidal compounds in stable formulations that can be easily stored for a long time and which still have a high stability and effective activity until end use. This problem especially occurs and may get worsen if more than one active compound is present in the composition.
Therefore, one object of the present invention is to provide improved herbicidal combination for weeds control in post emergence conditions along with an insecticide acting as a safener in the herbicidal composition which will reduce the unwanted phytotoxic effect on crops on post herbicide application. Another object of the present invention is to provide a method and a composition for controlling weeds in post emergence conditions.
Yet another object of the present invention is to provide improved combinations of improved broadleaf and grassy weed control without adversely affecting desirable plants and reducing the unwanted effect by using an insecticide(s) as a safener.
Embodiment of the present invention can ameliorate one or more of the above mentioned problems.
Inventors of the present invention have surprisingly found that the novel synergistic
herbicidal composition of a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grasses or mixture thereof; a one or more herbicide(s) selected from the group of various class of compounds for control of broad-leaved weeds and grasses in crops of useful plants or mixture thereof; and an insecticide selected from the class of diamide, metadiamide or isoxazoline as safener for reducing phytotoxicity in crops on post herbicide application or mixture thereof as described herein which can provide solution to the above mentioned problems.
SUMMARY OF THE INVENTION
Therefore an aspect of the present invention provides composition comprises with herbicidal compound or mixture thereof along with insectide as safener for reducing phytotoxicity in crops on post herbicide application.
Another aspect of the present invention provides a synergistic herbicidal composition comprising an insecticide(s) selected from the class of diamide, metadiamide or isoxazoline used as safener for reducing phytotoxicity in crops on post herbicide application.
Therefore an aspect of the present invention provides a synergistic herbicidal composition comprising bioactive amounts of (A) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grasses or mixture thereof; (B) a one or more herbicide(s) selected from the group of various class of compounds for control of broad-leaved weeds and grasses in crops of useful plants or mixture thereof; and (C) an insecticide selected from the class of diamide, metadiamide or isoxazoline as safener for reducing phytotoxicity in crops on post herbicide application or mixture thereof.
Further aspect of the present invention provides a synergistic herbicidal composition comprising bioactive amounts of (A) a herbicide from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grasses of Aryloxyphenoxy group is selected from propionate ('FOPs')-clodinafop-propargyl, cyhalofop-butyl, diclofop, fenoxaprop-P, fluazifop-P, haloxyfop, metamifop, propaquizafop, quizalofop-P-ethyl;of Cyclohexanedione ('DIMs') group is selected from alloxydim, butroxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, tepraloxydim; of Phenylpyrazoline ('DEN') group is selected from pinoxaden or mixture thereof; (B) a one or more herbicide(s) selected from the group of Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor, Synthetic Auxin, Inhibitor of photosynthesis at photosystem II site A, Inhibitor of photosynthesis at photosystem II site B, Inhibitor of lipid synthesis; not ACCase inhibition, Inhibitor of 5-enolypyruvyl-shikimate-3-phosphate synthase (EPSPS), Inhibitor of glutamine synthetase: Phosphonic acid, Inhibitor of phytoene desaturase (PDS), Inhibitor of 1-deoxy-D-xyulose 5-phosphate sunthatase (DOXP synthase), Inhibitor of protoporphyrinogen oxidase (Protox, PPO), Mitosis Inhibitor, Inhibitor of 7,8-dihydro-preroate synthetase (DHP), Inhibitor of indoleacetic acid transport, Inhibitor of cell wall synthesis site A, Inhibitor of cell wall synthesis site B, Inhibitor of cell wall synthesis site C, Inhibition of cellulose synthesis, Photosystem I electron diverter, Membrane disruptor (uncouplers), Inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD), Tyrosine Aminotransferase, Inhibition of dihydroorotate dehydrogenase(DHODH), HTS (homogentisate solanesyltransferase)-a downstream enzyme of HPPD, VLCAFE inhibitors, Inhibition of lycopene cyclase, Inhibition of Solanesyl Diphosphate Synthase (SDS), Inhibition of serine-threonine protein phosphatase or Herbicide with unknown mode of action or mixture thereof; and (C) an insecticide selected from the class of diamide, metadiamide or isoxazoline as safener for reducing phytotoxicity in crops on post herbicide application or mixture thereof.
In present aspect of the invention to provide a synergistic herbicidal composition comprising an insecticide selected from the class of diamide, metadiamide or isoxazoline as a safener in composition for reducing phytotoxicity in crops treated with a herbicide present in the present herbicidal composition.
In further aspect of the present invention provides a synergistic herbicidal composition comprising an insecticide(s) as a safener to promote speedy recovery of the crop or plant from herbicidal injury. Thus accordingly reduces the stress due to abiotic factors and thus promotes overall plant or crop health and there by plant or crop yield.
Accordingly, in a further aspect, the present invention to provide a combination and a method of controlling post-emergence weeds and provide a herbicidal combination for improved broadleaf and grassy weed control without adversely affecting desirable plants by reducing phytotoxicity in crops treated with a herbicide present in the present herbicidal composition.
Yet another aspect, the present invention provides to provide a herbicidal combination which reduces the amount of chemical herbicidal agent necessary to obtain the acceptable weed control.
Accordingly, the present invention relates to method which provides a broader spectrum of controlling weeds that helps in resistance management, thus preventing the weed from becoming resistant to either of the herbicides while providing a broader spectrum of control at lower use rates.
As per one embodiment formulation for the herbicidal composition is selected from Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion, oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule (GR) / Soil Applied Granules (SAG), Controlled release granules (CR); and and one or more customary formulation adjuvants such as a) dispersant, b) wetting agent, c) anti-foaming agent, d) biocides, e) anti-freezing agent, f) suspending agent, g) thickener, h) coating agent and i) buffering agent.
The remainder of the aqueous formulation is preferably wholly water but may comprise other materials, such as inorganic salts.
Accordingly, in a first aspect, the present invention provides a synergistic herbicidal compositions comprising bioactive amounts of (A) a herbicide from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grasses of Aryloxyphenoxy group is selected from propionate ('FOPs')-clodinafop-propargyl, cyhalofop-butyl, diclofop, fenoxaprop-P, fluazifop-P, haloxyfop, metamifop, propaquizafop, quizalofop-P-ethyl;of Cyclohexanedione ('DIMs') group is selected from alloxydim, butroxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, tepraloxydim; of Phenylpyrazoline ('DEN') group is selected from pinoxaden or mixture thereof; (B) a one or more herbicide(s) selected from the group of Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor, Synthetic Auxin, Inhibitor of photosynthesis at photosystem II site A, Inhibitor of photosynthesis at photosystem II site B, Inhibitor of lipid synthesis; not ACCase inhibition, Inhibitor of 5-enolypyruvyl-shikimate-3-phosphate synthase (EPSPS), Inhibitor of glutamine synthetase: Phosphonic acid, Inhibitor of phytoene desaturase (PDS), Inhibitor of 1-deoxy-D-xyulose 5-phosphate sunthatase (DOXP synthase), Inhibitor of protoporphyrinogen oxidase (Protox, PPO), Mitosis Inhibitor, Inhibitor of 7,8-dihydro-preroate synthetase (DHP), Inhibitor of indoleacetic acid transport, Inhibitor of cell wall synthesis site A, Inhibitor of cell wall synthesis site B, Inhibitor of cell wall synthesis site C, Inhibition of cellulose synthesis, Photosystem I electron diverter, Membrane disruptor (uncouplers), Inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD), Tyrosine Aminotransferase, Inhibition of dihydroorotate dehydrogenase(DHODH), HTS (homogentisate solanesyltransferase)-a downstream enzyme of HPPD, VLCAFE inhibitors, Inhibition of lycopene cyclase, Inhibition of Solanesyl Diphosphate Synthase (SDS), Inhibition of serine-threonine protein phosphatase or Herbicide with unknown mode of action or mixture thereof; and (C) an insecticide selected from the class of diamide, metadiamide or isoxazoline as safener for reducing phytotoxicity in crops on post herbicide application or mixture thereof and one or more customary formulation adjuvants; shows synergistic activity.

DETAILED DESCRIPTION OF THE INVENTION:
The term "synergistic", as used herein, refers the combined action of two or more active
agents blended together and administered conjointly that is greater than the sum of their
individual effects.
"Bioactive amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficient to effect such treatment.
For the purposes of the present invention, an insecticide(s) insecticide selected from the class of diamide, metadiamide or isoxazoline or mixture thereof is used as a ‘safener’ and the term ‘safener’ in present context is defined as substances which reduce or prevent the phytotoxic effect of crop protectants specifically herbicide, on plants treated therewith and/or on plants whose seeds and/or growth substrate have been treated or are treated therewith.
The term ‘herbicide’ is used herein to mean an active ingredient that kills, controls or otherwise adversely modifies the growth of unwanted plants. An herbicidally effective or vegetation controlling amount is an amount of active ingredient which causes an adversely modifying effect and includes deviations from natural development, killing, regulation, desiccation, retardation, and the like.
The term “phytotoxicity” as used herein means unintended herbicidal effect on a plant of interest resulting in significant damage to the plant. In an embodiment the present invention relates to use of a pyrethroid insecticide for reducing phytotoxicity in crops on post herbicide application.
Therefore an aspect of the present invention provides a synergistic herbicidal composition comprising bioactive amounts of (A) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grasses or mixture thereof; (B) a one or more herbicide(s) selected from the group of various class of compounds for control of broad-leaved weeds and grasses in crops of useful plants or mixture thereof; and (C) an insecticide selected from the class of diamide, metadiamide or isoxazoline as safener for reducing phytotoxicity in crops on post herbicide application or mixture thereof.
Further aspect of the present invention provides a synergistic herbicidal composition comprising bioactive amounts of (A) a herbicide from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grasses of Aryloxyphenoxy group is selected from propionate ('FOPs')-clodinafop-propargyl, cyhalofop-butyl, diclofop, fenoxaprop-P, fluazifop-P, haloxyfop, metamifop, propaquizafop, quizalofop-P-ethyl;of Cyclohexanedione ('DIMs') group is selected from alloxydim, butroxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, tepraloxydim; of Phenylpyrazoline ('DEN') group is selected from pinoxaden or mixture thereof; (B) a one or more herbicide(s) selected from the group of Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor, Synthetic Auxin, Inhibitor of photosynthesis at photosystem II site A, Inhibitor of photosynthesis at photosystem II site B, Inhibitor of lipid synthesis; not ACCase inhibition, Inhibitor of 5-enolypyruvyl-shikimate-3-phosphate synthase (EPSPS), Inhibitor of glutamine synthetase: Phosphonic acid, Inhibitor of phytoene desaturase (PDS), Inhibitor of 1-deoxy-D-xyulose 5-phosphate sunthatase (DOXP synthase), Inhibitor of protoporphyrinogen oxidase (Protox, PPO), Mitosis Inhibitor, Inhibitor of 7,8-dihydro-preroate synthetase (DHP), Inhibitor of indoleacetic acid transport, Inhibitor of cell wall synthesis site A, Inhibitor of cell wall synthesis site B, Inhibitor of cell wall synthesis site C, Inhibition of cellulose synthesis, Photosystem I electron diverter, Membrane disruptor (uncouplers), Inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD), Tyrosine Aminotransferase, Inhibition of dihydroorotate dehydrogenase(DHODH), HTS (homogentisate solanesyltransferase)-a downstream enzyme of HPPD, VLCAFE inhibitors, Inhibition of lycopene cyclase, Inhibition of Solanesyl Diphosphate Synthase (SDS), Inhibition of serine-threonine protein phosphatase or Herbicide with unknown mode of action or mixture thereof; and (C) an insecticide selected from the class of diamide, metadiamide or isoxazoline as safener for reducing phytotoxicity in crops on post herbicide application or mixture thereof.
In an embodiment of the present invention herbicide from Acetyl CoA Carboxylase (ACCase) Inhibitor of Aryloxyphenoxy-propionate ('FOPs') group is selected from clodinafop-propargyl, cyhalofop-butyl, diclofop, fenoxaprop-P, fluazifop-P, haloxyfop, metamifop, propaquizafop, quizalofop-P-ethyl; of Cyclohexanedione ('DIMs') group is selected from alloxydim, butroxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, tepraloxydim; Phenylpyrazoline ('DEN') such as pinoxaden or mixture thereof.
In an embodiment of the present invention herbicide of Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor from Sulfonylurea group is selected from amidosulfuron, azimsulfuron, bensulfuron methyl, chlorimuron ethyl, chlorsulfuron, cinosulfuron, cloransulfuron methyl, cyclosulfamuron, ethametsulfuron methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron methyl sodium, foramsulfuron, halosulfuron methyl, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron mehtyl, nicosufulfuron, primisulfuron methyl, prosulfuron, pyrazosulfuron ethyl, rimsulfuron, rimsulfuron, sulfometuron methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron methyl, trifloxysulfuron, triflusulfuron methyl.
In an embodiment of the present invention herbicide from Acetoacetate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor from bispyribac-sodium, pyribenzoxim, pyrimisulfan, pyrithiobac sodium; from Triazolopyrimidine group selected from cloransulam-methyl, diclosulam, florasulam, flumetsulam, penoxsulam, pyroxsulam.
In an embodiment of the present invention herbicide from Acetoacetate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor of Sulfonylaminocarbonyl group is selected from triazolinone-flucarbazone-sodium, propoxycarbazone-sodium, thiencarbazone-methyl; from Imidazolinone group such as imazamethabenz methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; from Sulfonanilides group is triafamone.
In an embodiment of the present invention herbicide from Synthetic Auxin of Phenoxy carboxylic acid group is selected from 2,4-D, MCPA, MCPB, mecoprop; of Pyrimidine carboxylic acid group is selected from aminocyclopyrachlor; of Pyridine carboxylic acid group is selected from aminopyralid, clopyralid, florpyrauxifen benzyl, fluroxypyr, picloram, triclopyr; of Benzoic acid group is dicamba; of Quinoline carboxylic acid group is quinclorac; and halauxifen methyl.
In an embodiment of the present invention herbicide from Inhibitor of photosynthesis at photosystem II site A of Phenyl carbamate is selected from desmedipham, phenmedipham; of Pyridazinone group is pyrazon; of Triazine group is selected from ametryn, atrazine, cyanazine, desmetryn, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazine, trietazine; of Triazinone group is selected from hexazione, metamitron, metribuzin; of Triazolinone group is amicarbazone; of Urea group is metoxuron; of Uracil group is bromacil, terbacil.
In an embodiment of the present invention herbicide from Inhibitor of photosynthesis at photosystem II site B of Benzothiadiazinone group is bentazone; of Nitrile group is selected from bromoxynil, ioxynil; of Phenyl-pyridazine group is pyridate.
In an embodiment of the present invention herbicide from Inhibitor of lipid synthesis; not ACCase inhibition of Benzofuran group is ethofumesate; of Phosphorodithioate group is bensulie; of Thiocarbamate group is selected from butylate, cycloate, EPTC, esprocarb, molinate, pebulate, prosulfocarb, thiobencarb, triallate, vernolate.
In an embodiment of the present invention herbicide from Inhibitor of 5-enolypyruvyl-shikimate-3-phosphate synthase (EPSPS) of Glycine group is Glyphosate.
In an embodiment of the present invention herbicide from Inhibitor of glutamine synthetase of Phosphonic acid group is glufosinate.
In an embodiment of the present invention herbicide from Inhibitor of phytoene desaturase (PDS) of Pyridinecarboxamide group is selected from diflufenican, picolinafen; of Pyridazinone group is norflurazon; and other compounds such as beflubutamid, fluridone, flurochloridone, flurtamone.
In an embodiment of the present invention herbicide from Inhibitor of 1-deoxy-D-xyulose 5-phosphate sunthatase (DOXP synthase) of Isoxazolidinone group is clomazone.
In an embodiment of the present invention herbicide from Inhibitor of protoporphyrinogen oxidase (Protox, PPO) of Dipheylether group is selected from aclifluorfen, bifenox, fluoroglycofen, fomesafen, lactofen, oxyfluorfen; of Triazolinone group is selected from azafenidin, carfentrazone-ethyl, flufenpyr-ethyl, sulfentrazone; of Pyrimidinedione group is selected from butafenacil, saflufenacil; of N-phenylphthalimide group is selected from flumiclorac, flumioxazin; of N-Phenyl-imide group is trifludimoxazin; of Thiadiazole group is fluthiacet-methyl; of Oxadiazole group is selected from oxadiargyl, oxadiazon; of Phenylpyrazole group is pyraflufen-ethyl, of other group is pyraclonil; of Uracil group is tiafenacil; of Pyrazole group is cyclopyranil.
In an embodiment of the present invention herbicide from Mitosis Inhibitor of Chloroacetamide group is selected from acetochlor, alachlor, butachlor, dimethenamid, metazachlor, pretilachlor, propachlor, s-metolachlor, thenylchlor; of Tetrazolinone group is fentrazamide; of Oxyacetamide group is selected from flufenacet, mefenacet; of Acetamide group is napropamide; of Carbamate group is carbetamide; and of other group is anilofos.
In an embodiment of the present invention herbicide from Inhibitor of 7,8-dihydro-preroate synthetase (DHP) of Carbamate group is asulam.
In an embodiment of the present invention herbicide from Inhibitor of indoleacetic acid transport of Phthalamate semicarbazone group is selected from diflufenzopyr, naptalam.
In an embodiment of the present invention herbicide from Inhibitor of cell wall synthesis site A of Nitrile group is selected from dichlobenil.
In an embodiment of the present invention herbicide from Inhibitor of cell wall synthesis site B of Benzamide group is selected from Isoxaben.
In an embodiment of the present invention herbicide from Inhibitor of cell wall synthesis site C of Alkylazines group is selected from indaziflam, triaziflam.
In an embodiment of the present invention herbicide from Inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD) of Pyrazole group is selected from benzofenap, pyrasulfotole, pyrazolynate, pyrazoxyfen, tolpyralate; of Benzoylbicyclooctanedione group is benzobicyclon; Triketone group is selected from mesotrione, tembotrione, sulcotrione, tefuryltrione, fenquinotrione, lancotrione sodium; of Isoxazoles group is selected from isoxaflutole; bicyclo ring compound group is bicyclopyrone.
In an embodiment of the present invention herbicide from Tyrosine Aminotransferase is selected from cinmethylin, methiozolin.
In an embodiment of the present invention herbicide from Inhibitors of dihydroorotate dehydrogenase (DHODH) is tetflupyrolimet.
In an embodiment of the present invention herbicide from HTS (homogentisate solanesyltransferase)-a downstream enzyme of HPPD is cyclopyrimorate.
In an embodiment of the present invention herbicide from VLCAFE inhibitors of Isoxazoline group is pyroxasulfone, of Triazolinone group is ipfencarbazone, of Trifluoromethansulfonanilides group is dimesulfazet, and other compounds such as fenoxasulfone.
In an embodiment of the present invention herbicide from Inhibitors of Solanesyl Diphosphate Synthase (SDS) is aclonifen.
In an embodiment of the present invention herbicide from Inhibitors of lycopene cyclase is amitrole.
In an embodiment of the present invention herbicide from Inhibitors of serine-threonine protein phosphatase is endothall.
In an embodiment of the present invention herbicide with unknown mode of action is selected from bromobutide, pelargonic acid, diphenamid, naproanilide, dalapon, copper (salt), epyrifenacil, bixzolone.
In an embodiment of the present invention an insecticide for reducing phytotoxicity in crops on post herbicide application of diamides class is selectede from chlorantraniliprole, cyantraniliprole, cyclaniliprole, cyhalodiamide, cyproflanilide, flubendiamide, tetraniliprole, tetrachlorantraniliprole, tyclopyrazoflor; of class of metadiamides is broflanilide; of class of isoxazolines is selected from fluxametamide, isocycloseram.
1. Acetyl CoA Carboxylase (ACCase) Inhibitors:
(a) Aryloxyphenoxy-propionate ('FOPs'):
Clodinafop-propargyl is a carboxylic ester resulting from the formal condensation of the carboxy group of clodinafop with the hydroxy group of prop-2-yn-1-ol. It is widely used as a herbicide for the control of annual grass weeds in cereal crops. It has a role as an EC 6.4.1.2 (acetyl-CoA carboxylase) inhibitor, a herbicide and an agrochemical. It is a carboxylic ester, an aromatic ether, an organochlorine compound, an organofluorine compound, a member of pyridines and a propyzamide. It derives from a prop-2-yn-1-ol and a clodinafop. It has IUPAC name as prop-2-ynyl (2R)-2-[4-(5-chloro-3-fluoropyridin-2-yl)oxyphenoxy]propanoate.
Cyhalofop-butyl is an aromatic ether. Cyhalofop-butyl is a post-emergence, aryloxy phenoxy propionate herbicide, which is used in controlling weeds in rice plantations. Its mode of action involves the inhibition of acetyl-coenzyme A carboxylase (ACCase) biosynthesis. It has an IUPAC name as butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoate.
Metamifop is a 2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}-N-(2-fluoro phenyl)-N-methylpropanamide that has R-configuration. It is an inhibitor of acetyl-coenzyme A carboxylase (ACCase) and a postemergence herbicide which exhibits high control efficacy against sensitive weeds, especially Echinochloa crus-galli in paddy fields. It has a role as an EC 6.4.1.2 (acetyl-CoA carboxylase) inhibitor and a phenoxy herbicide. It is an enantiomer of a (S)-metamifop. It has IUPAC name as (2R)-2-[4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy]-N-(2-fluorophenyl)-N-methylpropanamide.
Propaquizafop is a Acetyl CoA Carboxylase (ACCase) Inhibitor. It has an IUPAC name as 2-(propan-2-ylideneamino)oxyethyl 2-[4-(6-chloroquinoxalin-2yl) oxy phenoxy] propa- noate.
Quizalofop-P-ethyl is an ethyl 2-{4-[(6-chloroquinoxalin-2-yl)oxy]phenoxy} propanoate that has R configuration. A proherbicide for quizalofop-P, it is used to control annual and perennial grass weeds in a variety of crops, including potatoes, sugar beet, peanuts, cotton and flax. It has a role as a proherbicide and an agrochemical. It is an ethyl 2-{4-[(6-chloroquinoxalin-2-yl)oxy]phenoxy}propanoate and a quinoxaline herbicide. It derives from a quizalofop-P. It is an enantiomer of a (S)-quizalofop-ethyl. It has IUPAC name as ethyl (2R)-2-[4-(6-chloroquinoxalin-2-yl)oxyphenoxy] propanoate.
(b) Phenylpyrazoline ('DEN')-
Pinoxaden is a pyrazolooxadiazepine that is 7-oxo-1,2,4,5-tetrahydro-7H-pyrazolo[1,2-d][1,4,5]oxadiazepin which is substituted at positions 8 and 9 by 2,6-diethyl-4-methylphenyl and pivaloyloxy groups, respectively. A pro-herbicide (by hydrolysis of the pivalate ester to give the corresponding enol), it is used for control of grass weeds in cereal crops. It has a role as a xenobiotic, an environmental contaminant, an agrochemical, an EC 6.4.1.2 (acetyl-CoA carboxylase) inhibitor and a pro-herbicide. It is a pivalate ester and a pyrazolooxadiazepine. It derives from a pinoxaden acid. It has an IUPAC name as [8-(2,6-diethyl-4-methylphenyl)-7-oxo-1,2,4,5-tetrahydropyrazolo[1,2-d][1,4,5]oxadiazepin-9-yl] 2,2-dimethylpropanoate.
2. Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor:
(a) Pyrimidinyl (thio) benzoate:
Bispyribac-sodium is a herbicide from class of Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor. It has IUPAC name as sodium; 2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate. It has been used as a Pesticides used to destroy unwanted vegetation, especially various types of weeds, grasses (POACEAE), and woody plants.
Triazolopyrimidine: Penoxsulam is a member of triazolopyrimidines. It has an IUPAC name as 2-(2,2-difluoroethoxy)-N-(5,8-dimethoxy-[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)-6-(trifluoro meth yl) benzenesulfonamide. These herbicides inhibit the enzyme acetolactate synthase (ALS).
Imidazolinone: Imazethapyr is a selective herbicide that can be applied as an early pre-plant, pre-plant incorporated, pre-emergent or post-emergent treatment in various crops. The application method depends upon the crop, anticipated weed spectrum and the preference of the applicator. When Imazethapyr is applied post-emergence, absorption may occur through both the roots and foliage. It has an IUPAC name as 5-ethyl-2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl)pyridine-3-carboxylic acid. Absorbed by plant roots and foliage, being translocated to meristematic regions where it inhibits the biosynthesis of valine, leucine and isoleucine preventing cell division.
Sulfonanilides: Triafamone is a new sulfonanilide herbicide. Its mode of action is inhibition of the enzyme acetolactate synthase (ALS). It has been effectively used in direct seeded or transplanted rice from seeding or transplanting to late post-emergence at rates of 20 to 50 g a.i./ha using spray or granular formulations. Target weeds are important grasses such as Echinochloa crus-galli, Echinochloa colonum, Echinochloa oryzicola, Paspalum distichum, Isachne globosa, and sedges (including ALS resistant strains). It has an IUPAC name as N-[2-(4,6-dimethoxy-1,3,5-triazine-2-carbonyl)-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide.
3. Inhibitor of protoporphyrinogen oxidase (Protox, PPO):
(a) Dipheylether:
Aclifluorfen is a member of the class of benzoic acids that is 2-nitrobenzoic acid in which the hydrogen at position 5 is replaced by a 2-chloro-4-(trifluoromethyl)phenoxy group. It is a herbicide used for the post-emergence control of a variety of annual broadleaf weeds. It has a role as a herbicide, an agrochemical and protoporphyrinogen oxidase inhibitor. It is a member of benzoic acids, an organochlorine compound, an organofluorine compound, an aromatic ether, a monocarboxylic acid and a C-nitro compound. It has an IUPAC name as 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid.
Fomesafen is an N-sulfonylcarboxamide that is N-(methylsulfonyl)benzamide in which the phenyl ring is substituted by a nitro group at position 2 and a 2-chloro-4-(trifluoromethyl)phenoxy group at position 5. A protoporphyrinogen oxidase inhibitor, it was specially developed for use (generally as the corresponding sodium salt, fomesafen-sodium) for post-emergence control of broad-leaf weeds in soya. It has a role as a herbicide, an agrochemical and an EC 1.3.3.4 (protoporphyrinogen oxidase) inhibitor. It is an aromatic ether, a N-sulfonylcarboxamide, a C-nitro compound, an organofluorine compound, a member of monochlorobenzenes and a member of phenols. It has IUPAC name as 5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-methylsulfonyl-2-nitrobenzamide.
Triazolinone:
Carfentrazone-ethyl is an ethyl ester resulting from the formal condensation of the carboxy group of 2-chloro-3-{2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]-4-fluorophenyl}propanoic acid with ethanol. It has a role as a proherbicide. It is used to destroy unwanted vegetation, especially various types of weeds, grasses (POACEAE), and woody plants.
Thiadiazole:
Fluthiacet-methyl is a methyl ester resulting from the formal condensation of the carboxy group of fluthiacet with methanol. A proherbicide for fluthiacet, it is used for the control of broad-leaved weeds in crops such as maize and soya. It has a role as an agrochemical, an EC 1.3.3.4 (protoporphyrinogen oxidase) inhibitor and a proherbicide. It is an organic sulfide, a methyl ester, a member of monochlorobenzenes, a member of monofluorobenzenes and a thiadiazolopyridazine. It derives from a fluthiacet. It has an IUPAC name as methyl 2-[2-chloro-4-fluoro-5-[(3-oxo-5,6,7,8-tetrahydro-[1,3,4]thiadiazolo[3,4-a]pyridazin-1-ylidene)amino]phenyl]sulfanylacetate.
4. Inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD):
(a) Pyrazole:
Tolpyralate is a benzoylpyrazole that is 1H-pyrazole substituted by an ethyl, 3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl, and 1-[(methoxycarbonyl)oxy] ethoxy groups at positions 1, 4 and 5, respectively. It is an aromatic ether, a benzoylpyrazole, a carbonate ester, a member of toluenes, an aromatic ketone and a sulfone. It has IUPAC name as 1-[2-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-methylsulfonylbenzoyl]pyrazol-3-yl]oxyethyl methyl carbonate.
(b) Triketone:
Mesotrione is an aromatic ketone that is cyclohexa-1,3-dione in which one of the hydrogens at position 2 is substituted by a 4-(methanesulfonyl)-2-nitrobenzoyl group. It has a role as a herbicide, an EC 1.13.11.27 (4-hydroxyphenylpyruvate dioxygenase) inhibitor, a xenobiotic, an environmental contaminant and a carotenoid biosynthesis inhibitor. It is a sulfone, a C-nitro compound, an aromatic ketone and a beta-triketone. It derives from a benzophenone. It has an IUPAC name as 2-(4-methylsulfonyl-2-nitrobenzoyl)cyclohexane-1,3-dione.
Tembotrione is an aromatic ketone that is 2-benzoylcyclohexane-1,3-dione in which the phenyl group is substituted at positions 2, 3, and 4 by chlorine, (2,2,2-trifluoroethoxy)methyl, and methylsulfonyl groups, respectively. It is a post-emergence herbicide used (particularly in conjunction with the herbicide safener cyprosulfamide) for the control of a wide range of broad-leaved and grassy weeds in corn and other crops. It has a role as a herbicide, an agrochemical, an EC 1.13.11.27 (4-hydroxyphenylpyruvate dioxygenase) inhibitor and a carotenoid biosynthesis inhibitor. It is a sulfone, a cyclic ketone, an aromatic ketone, a member of monochlorobenzenes, an organofluorine compound, an ether and a beta-triketone. It has an IUPAC name as 2-[2-chloro-4-methylsulfonyl-3-(2, 2, 2-trifluoroethoxymethyl) benzoyl] cyclohexane 1, 3-dione.
5. Inhibition of dihydroorotate dehydrogenase (DHODH):
Tetflupyrolimet is a new aryl pyrrolidinone anilide chemical class) for grass control in rice. The target site is dihydroorotate dehydrogenase, a key enzyme in pyrimidine biosynthesis It ha IUPAC name as (3S, 4S)-2'-fluoro-1-methyl-2-oxo-4-[3-(trifluoromethyl) phenyl]pyrrolidine-3-carboxanilide. It effectively control economically important monocotyledonous and dicotyledonous weeds while safe to wheat, corn and rice.
6. VLCAFE inhibitors:
(a) Trifluoromethansulfonanilides:
Dimesulfazet is sulfonamide along with VLCFAE-inhibiting herbicides. It has an IUPAC name as 2'-[(3,3-dimethyl-2-oxoazetidin-1-yl)methyl]-1,1,1-trifluoromethane sulfona nilide.
7. Herbicide with unknown mode of action:
Bromobutide is a monocarboxylic acid amide having a 2-phenylpropan-2-yl substituent attached to the amide nitrogen and a 1-bromo-2,2-dimethylpropyl group attached to the carbonyl carbon. It has a role as a herbicide. It is a monocarboxylic acid amide and an organobromine compound. It has an IUPAC name as 2-bromo-3,3-dimethyl-N-(2-phenylpropan-2-yl)butanamide.
8. Insecticides from the class of diamides:
Chlorantraniliprole is a carboxamide resulting from the formal condensation of the carboxylic acid group of 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid with the primary amino group of 2-amino-5-chloro-N,3-dimethylbenzamide. The first of the anthranilic diamide insecticides, it is a ryanodine receptor activator and is used to protect a wide variety of crops, including corn, cotton, grapes, rice and potatoes. It has a role as a ryanodine receptor agonist. It is an organobromine compound, a member of pyridines, a member of pyrazoles, a pyrazole insecticide, a member of monochlorobenzenes and a secondary carboxamide. It has an IUPAC name as 5-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloropyridin-2-yl)pyrazole-3-carb oxamide.
Cyantraniliprole is a carboxamide that is chlorantraniliprole in which the chlorine atom attached to the phenyl ring has been replaced by a cyano group. A ryanodine receptor agonist, it is used as insecticide for the control of whitefly, thrips, aphids, fruitflies, and fruit worms in crops such as onions, potatoes and tomatoes. It is highly toxic to honeybees. It has a role as a ryanodine receptor agonist. It is a pyrazole insecticide, a nitrile, an organochlorine compound, an organobromine compound, a member of pyridines and a secondary carboxamide. It has an IUPAC name as 5-bromo-2-(3-chloropyridin-2-yl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]pyrazole-3-carboxamide.
9. Insecticides from the class of metadiamides:
Broflanilide is a benzamide obtained by formal condensation of the carboxy group of 3-[benzoyl(methyl)amino]-2-fluorobenzoic acid with the amino group of 2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)aniline. An insecticide that exhibits high larvicidal activity against Spodoptera litura and is effective against pests with resistance to cyclodienes and fipronil It has a role as an agrochemical and a GABA antagonist. It is a member of benzamides, a member of monofluorobenzenes, an organofluorine insecticide, a member of bromobenzenes and a member of (trifluoromethyl)benzenes. It has an IUPAC name as 3-[benzoyl(methyl)amino]-N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl]-2-fluoro benz amide.
10. Insecticide from the class of Isoxazolines:
Fluxametamide is a benzamide obtained by formal condensation of the carboxy group of 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-2 met- hyl benzoic acid with the amino group of N-methoxymethanimidamide. It is a member of benzamides, an isoxazoline, a dichlorobenzene, a member of formamidines, an organofluorine compound and an ether. It has IUPAC name as 4-[5-(3, 5-dichlorophenyl)-5-(trifluoromethyl)-4H-1, 2-oxazol-3-yl]-N-[(E)-methoxyimino met- hyl]-2-methyl benzam- ide.
The present inventors believe that the combination of the present invention surprisingly results in a synergistic action. The combination of the present invention allows for a broad spectrum of weed control and hence has surprisingly improved plant vigour and yield. The broad spectrum of the present combination of controlling weeds that also provides a solution for in resistance management, thus preventing the weed from becoming resistant to either of the herbicides while providing a broader spectrum of control at lower use rates.
The synergistic composition has very advantageous curative, preventive herbicidal properties for protecting cultivated plants. As has been mentioned, said active ingredient composition can be used to inhibit or destroy and effective management of the controlling pre-emergence and post-emergence weeds. The synergistic composition comprising herbicidal compounds for management and control of broad-leaved weeds and grasses in crops of useful plants.
The present synergistic herbicidal composition further comprises of an insecticide(s), play a very crucial role in protection of plant or crops of interest. An insecticide(s) in present composition reduces the phytotoxicity in crops on post herbicide application and promotes speedy recovery of the crop or plant from herbicidal injury. Thus accordingly reduces the stress due to abiotic factors and thus promotes overall plant or crop health and there by plant or crop yield.
Therefor the aspect of the present invention provides the herbicidal compositions comprising bioactive amounts of (A) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grasses or mixture thereof; (B) a one or more herbicide(s) selected from the group of various class of compounds for control of broad-leaved weeds and grasses in crops of useful plants or mixture thereof; and (C) an insecticide selected from the class of diamide, metadiamide or isoxazoline or mixture thereof as safener for reducing phytotoxicity in crops tre on post herbicide application; are present in most preferred combinations as below:
Compound A Acetyl CoA Carboxylase (ACCase) Inhibitor Compound B Herbicide(s) Compound C An Insecticide from the class of diamide, metadiamide, isoxazoline as safener
Clodinafop Propargyl Acifluorfen Chlorantraniliprole
Clodinafop Propargyl Acifluorfen Cyantraniliprole
Clodinafop Propargyl Acifluorfen Cyclaniliprole
Clodinafop Propargyl Acifluorfen Tetraniliprole
Clodinafop Propargyl Acifluorfen Broflanilide
Clodinafop Propargyl Acifluorfen Isocycloseram
Clodinafop Propargyl Fomesafen Chlorantraniliprole
Clodinafop Propargyl Fomesafen Cyantraniliprole
Clodinafop Propargyl Fomesafen Cyclaniliprole
Clodinafop Propargyl Fomesafen Tetraniliprole
Clodinafop Propargyl Fomesafen Broflanilide
Clodinafop Propargyl Fomesafen Isocycloseram
Clodinafop Propargyl Fluthiacet methyl Chlorantraniliprole
Clodinafop Propargyl Fluthiacet methyl Cyantraniliprole
Clodinafop Propargyl Fluthiacet methyl Cyclaniliprole
Clodinafop Propargyl Fluthiacet methyl Tetraniliprole
Clodinafop Propargyl Fluthiacet methyl Broflanilide
Clodinafop Propargyl Fluthiacet methyl Isocycloseram
Clodinafop Propargyl Halauxifen methyl Chlorantraniliprole
Clodinafop Propargyl Halauxifen methyl Cyantraniliprole
Clodinafop Propargyl Halauxifen methyl Cyclaniliprole
Clodinafop Propargyl Halauxifen methyl Tetraniliprole
Clodinafop Propargyl Halauxifen methyl Broflanilide
Clodinafop Propargyl Halauxifen methyl Isocycloseram
Quizalofop-P-Ethyl Acifluorfen Chlorantraniliprole
Quizalofop-P-Ethyl Acifluorfen Cyantraniliprole
Quizalofop-P-Ethyl Acifluorfen Cyclaniliprole
Quizalofop-P-Ethyl Acifluorfen Tetraniliprole
Quizalofop-P-Ethyl Acifluorfen Broflanilide
Quizalofop-P-Ethyl Acifluorfen Isocycloseram
Quizalofop-P-Ethyl Fomesafen Chlorantraniliprole
Quizalofop-P-Ethyl Fomesafen Cyantraniliprole
Quizalofop-P-Ethyl Fomesafen Cyclaniliprole
Quizalofop-P-Ethyl Fomesafen Tetraniliprole
Quizalofop-P-Ethyl Fomesafen Broflanilide
Quizalofop-P-Ethyl Fomesafen Isocycloseram
Quizalofop-P-Ethyl Fluthiacet methyl Chlorantraniliprole
Quizalofop-P-Ethyl Fluthiacet methyl Cyantraniliprole
Quizalofop-P-Ethyl Fluthiacet methyl Cyclaniliprole
Quizalofop-P-Ethyl Fluthiacet methyl Tetraniliprole
Quizalofop-P-Ethyl Fluthiacet methyl Broflanilide
Quizalofop-P-Ethyl Fluthiacet methyl Isocycloseram
Quizalofop-P-Ethyl Halauxifen methyl Chlorantraniliprole
Quizalofop-P-Ethyl Halauxifen methyl Cyantraniliprole
Quizalofop-P-Ethyl Halauxifen methyl Cyclaniliprole
Quizalofop-P-Ethyl Halauxifen methyl Tetraniliprole
Quizalofop-P-Ethyl Halauxifen methyl Broflanilide
Quizalofop-P-Ethyl Halauxifen methyl Isocycloseram
Propaquizafop Acifluorfen Chlorantraniliprole
Propaquizafop Acifluorfen Cyantraniliprole
Propaquizafop Acifluorfen Cyclaniliprole
Propaquizafop Acifluorfen Tetraniliprole
Propaquizafop Acifluorfen Broflanilide
Propaquizafop Acifluorfen Isocycloseram
Propaquizafop Fomesafen Chlorantraniliprole
Propaquizafop Fomesafen Cyantraniliprole
Propaquizafop Fomesafen Cyclaniliprole
Propaquizafop Fomesafen Tetraniliprole
Propaquizafop Fomesafen Broflanilide
Propaquizafop Fomesafen Isocycloseram
Propaquizafop Fluthiacet methyl Chlorantraniliprole
Propaquizafop Fluthiacet methyl Cyantraniliprole
Propaquizafop Fluthiacet methyl Cyclaniliprole
Propaquizafop Fluthiacet methyl Tetraniliprole
Propaquizafop Fluthiacet methyl Broflanilide
Propaquizafop Fluthiacet methyl Isocycloseram
Propaquizafop Halauxifen methyl Chlorantraniliprole
Propaquizafop Halauxifen methyl Cyantraniliprole
Propaquizafop Halauxifen methyl Cyclaniliprole
Propaquizafop Halauxifen methyl Tetraniliprole
Propaquizafop Halauxifen methyl Broflanilide
Propaquizafop Halauxifen methyl Isocycloseram
Propaquizafop Imazethapyr Chlorantraniliprole
Propaquizafop Imazethapyr Cyantraniliprole
Propaquizafop Imazethapyr Cyclaniliprole
Propaquizafop Imazethapyr Tetraniliprole
Propaquizafop Imazethapyr Broflanilide
Propaquizafop Imazethapyr Isocycloseram
Metamifop Acifluorfen Chlorantraniliprole
Metamifop Acifluorfen Cyantraniliprole
Metamifop Acifluorfen Cyclaniliprole
Metamifop Acifluorfen Tetraniliprole
Metamifop Acifluorfen Broflanilide
Metamifop Acifluorfen Isocycloseram
Metamifop Fomesafen Chlorantraniliprole
Metamifop Fomesafen Cyantraniliprole
Metamifop Fomesafen Cyclaniliprole
Metamifop Fomesafen Tetraniliprole
Metamifop Fomesafen Broflanilide
Metamifop Fomesafen Isocycloseram
Metamifop Fluthiacet methyl Chlorantraniliprole
Metamifop Fluthiacet methyl Cyantraniliprole
Metamifop Fluthiacet methyl Cyclaniliprole
Metamifop Fluthiacet methyl Tetraniliprole
Metamifop Fluthiacet methyl Broflanilide
Metamifop Fluthiacet methyl Isocycloseram
Metamifop Halauxifen methyl Chlorantraniliprole
Metamifop Halauxifen methyl Cyantraniliprole
Metamifop Halauxifen methyl Cyclaniliprole
Metamifop Halauxifen methyl Tetraniliprole
Metamifop Halauxifen methyl Broflanilide
Metamifop Halauxifen methyl Isocycloseram
Metamifop Pyrazosulfuron ethyl Chlorantraniliprole
Metamifop Pyrazosulfuron ethyl Cyantraniliprole
Metamifop Pyrazosulfuron ethyl Cyclaniliprole
Metamifop Pyrazosulfuron ethyl Tetraniliprole
Metamifop Pyrazosulfuron ethyl Broflanilide
Metamifop Pyrazosulfuron ethyl Isocycloseram
Metamifop Bispyribac sodium Chlorantraniliprole
Metamifop Bispyribac sodium Cyantraniliprole
Metamifop Bispyribac sodium Cyclaniliprole
Metamifop Bispyribac sodium Tetraniliprole
Metamifop Bispyribac sodium Broflanilide
Metamifop Bispyribac sodium Isocycloseram
Metamifop Pyribenzoxim Chlorantraniliprole
Metamifop Pyribenzoxim Cyantraniliprole
Metamifop Pyribenzoxim Cyclaniliprole
Metamifop Pyribenzoxim Tetraniliprole
Metamifop Pyribenzoxim Broflanilide
Metamifop Pyribenzoxim Isocycloseram
Metamifop Penoxsulam Chlorantraniliprole
Metamifop Penoxsulam Cyantraniliprole
Metamifop Penoxsulam Cyclaniliprole
Metamifop Penoxsulam Tetraniliprole
Metamifop Penoxsulam Broflanilide
Metamifop Penoxsulam Isocycloseram
Metamifop Triafamone Chlorantraniliprole
Metamifop Triafamone Cyantraniliprole
Metamifop Triafamone Cyclaniliprole
Metamifop Triafamone Tetraniliprole
Metamifop Triafamone Broflanilide
Metamifop Triafamone Isocycloseram
Metamifop Florpyrauxifen benzyl Chlorantraniliprole
Metamifop Florpyrauxifen benzyl Cyantraniliprole
Metamifop Florpyrauxifen benzyl Cyclaniliprole
Metamifop Florpyrauxifen benzyl Tetraniliprole
Metamifop Florpyrauxifen benzyl Broflanilide
Metamifop Florpyrauxifen benzyl Isocycloseram
Metamifop Bentazone Chlorantraniliprole
Metamifop Bentazone Cyantraniliprole
Metamifop Bentazone Cyclaniliprole
Metamifop Bentazone Tetraniliprole
Metamifop Bentazone Broflanilide
Metamifop Bentazone Isocycloseram
Metamifop Carfentrazone ethyl Chlorantraniliprole
Metamifop Carfentrazone ethyl Cyantraniliprole
Metamifop Carfentrazone ethyl Cyclaniliprole
Metamifop Carfentrazone ethyl Tetraniliprole
Metamifop Carfentrazone ethyl Broflanilide
Metamifop Carfentrazone ethyl Isocycloseram
Metamifop Sulfentrazone Chlorantraniliprole
Metamifop Sulfentrazone Cyantraniliprole
Metamifop Sulfentrazone Cyclaniliprole
Metamifop Sulfentrazone Tetraniliprole
Metamifop Sulfentrazone Broflanilide
Metamifop Sulfentrazone Isocycloseram
Metamifop Tetflupyrolimet Chlorantraniliprole
Metamifop Tetflupyrolimet Cyantraniliprole
Metamifop Tetflupyrolimet Cyclaniliprole
Metamifop Tetflupyrolimet Tetraniliprole
Metamifop Tetflupyrolimet Broflanilide
Metamifop Tetflupyrolimet Isocycloseram
Metamifop Cyclopyrimorate Chlorantraniliprole
Metamifop Cyclopyrimorate Cyantraniliprole
Metamifop Cyclopyrimorate Cyclaniliprole
Metamifop Cyclopyrimorate Tetraniliprole
Metamifop Cyclopyrimorate Broflanilide
Metamifop Cyclopyrimorate Isocycloseram
Metamifop Ipfencarbazone Chlorantraniliprole
Metamifop Ipfencarbazone Cyantraniliprole
Metamifop Ipfencarbazone Cyclaniliprole
Metamifop Ipfencarbazone Tetraniliprole
Metamifop Ipfencarbazone Broflanilide
Metamifop Ipfencarbazone Isocycloseram
Metamifop Fenoxasulfone Chlorantraniliprole
Metamifop Fenoxasulfone Cyantraniliprole
Metamifop Fenoxasulfone Cyclaniliprole
Metamifop Fenoxasulfone Tetraniliprole
Metamifop Fenoxasulfone Broflanilide
Metamifop Fenoxasulfone Isocycloseram
Metamifop Pyroxasulfone Chlorantraniliprole
Metamifop Pyroxasulfone Cyantraniliprole
Metamifop Pyroxasulfone Cyclaniliprole
Metamifop Pyroxasulfone Tetraniliprole
Metamifop Pyroxasulfone Broflanilide
Metamifop Pyroxasulfone Isocycloseram
Metamifop Tefuryltrione Chlorantraniliprole
Metamifop Tefuryltrione Cyantraniliprole
Metamifop Tefuryltrione Cyclaniliprole
Metamifop Tefuryltrione Tetraniliprole
Metamifop Tefuryltrione Broflanilide
Metamifop Tefuryltrione Isocycloseram
Metamifop Fenquinotrione Chlorantraniliprole
Metamifop Fenquinotrione Cyantraniliprole
Metamifop Fenquinotrione Cyclaniliprole
Metamifop Fenquinotrione Tetraniliprole
Metamifop Fenquinotrione Broflanilide
Metamifop Fenquinotrione Isocycloseram
Metamifop Lancotrione sodium Chlorantraniliprole
Metamifop Lancotrione sodium Cyantraniliprole
Metamifop Lancotrione sodium Cyclaniliprole
Metamifop Lancotrione sodium Tetraniliprole
Metamifop Lancotrione sodium Broflanilide
Metamifop Lancotrione sodium Isocycloseram
Metamifop Tiafenacil Chlorantraniliprole
Metamifop Tiafenacil Cyantraniliprole
Metamifop Tiafenacil Cyclaniliprole
Metamifop Tiafenacil Tetraniliprole
Metamifop Tiafenacil Broflanilide
Metamifop Tiafenacil Isocycloseram
Metamifop Cyclopyranil Chlorantraniliprole
Metamifop Cyclopyranil Cyantraniliprole
Metamifop Cyclopyranil Cyclaniliprole
Metamifop Cyclopyranil Tetraniliprole
Metamifop Cyclopyranil Broflanilide
Metamifop Cyclopyranil Isocycloseram
Cyhalofop butyl Acifluorfen Chlorantraniliprole
Cyhalofop butyl Acifluorfen Cyantraniliprole
Cyhalofop butyl Acifluorfen Broflanilide
Cyhalofop butyl Acifluorfen Tetraniliprole
Cyhalofop butyl Fomesafen Chlorantraniliprole
Cyhalofop butyl Fomesafen Cyantraniliprole
Cyhalofop butyl Fomesafen Broflanilide
Cyhalofop butyl Fomesafen Tetraniliprole
Cyhalofop butyl Fluthiacet methyl Chlorantraniliprole
Cyhalofop butyl Fluthiacet methyl Cyantraniliprole
Cyhalofop butyl Fluthiacet methyl Cyclaniliprole
Cyhalofop butyl Fluthiacet methyl Tetraniliprole
Cyhalofop butyl Fluthiacet methyl Broflanilide
Cyhalofop butyl Fluthiacet methyl Isocycloseram
Cyhalofop butyl Halauxifen methyl Chlorantraniliprole
Cyhalofop butyl Halauxifen methyl Cyantraniliprole
Cyhalofop butyl Halauxifen methyl Cyclaniliprole
Cyhalofop butyl Halauxifen methyl Tetraniliprole
Cyhalofop butyl Halauxifen methyl Broflanilide
Cyhalofop butyl Halauxifen methyl Isocycloseram
Cyhalofop butyl Pyrazosulfuron ethyl Chlorantraniliprole
Cyhalofop butyl Pyrazosulfuron ethyl Cyantraniliprole
Cyhalofop butyl Pyrazosulfuron ethyl Cyclaniliprole
Cyhalofop butyl Pyrazosulfuron ethyl Tetraniliprole
Cyhalofop butyl Pyrazosulfuron ethyl Broflanilide
Cyhalofop butyl Pyrazosulfuron ethyl Isocycloseram
Cyhalofop butyl Bispyribac sodium Chlorantraniliprole
Cyhalofop butyl Bispyribac sodium Cyantraniliprole
Cyhalofop butyl Bispyribac sodium Cyclaniliprole
Cyhalofop butyl Bispyribac sodium Tetraniliprole
Cyhalofop butyl Bispyribac sodium Broflanilide
Cyhalofop butyl Bispyribac sodium Isocycloseram
Cyhalofop butyl Pyribenzoxim Chlorantraniliprole
Cyhalofop butyl Pyribenzoxim Cyantraniliprole
Cyhalofop butyl Pyribenzoxim Cyclaniliprole
Cyhalofop butyl Pyribenzoxim Tetraniliprole
Cyhalofop butyl Pyribenzoxim Broflanilide
Cyhalofop butyl Pyribenzoxim Isocycloseram
Cyhalofop butyl Penoxsulam Chlorantraniliprole
Cyhalofop butyl Penoxsulam Cyantraniliprole
Cyhalofop butyl Penoxsulam Cyclaniliprole
Cyhalofop butyl Penoxsulam Tetraniliprole
Cyhalofop butyl Penoxsulam Broflanilide
Cyhalofop butyl Penoxsulam Isocycloseram
Cyhalofop butyl Triafamone Chlorantraniliprole
Cyhalofop butyl Triafamone Cyantraniliprole
Cyhalofop butyl Triafamone Cyclaniliprole
Cyhalofop butyl Triafamone Tetraniliprole
Cyhalofop butyl Triafamone Broflanilide
Cyhalofop butyl Triafamone Isocycloseram
Cyhalofop butyl Florpyrauxifen benzyl Chlorantraniliprole
Cyhalofop butyl Florpyrauxifen benzyl Cyantraniliprole
Cyhalofop butyl Florpyrauxifen benzyl Cyclaniliprole
Cyhalofop butyl Florpyrauxifen benzyl Tetraniliprole
Cyhalofop butyl Florpyrauxifen benzyl Broflanilide
Cyhalofop butyl Florpyrauxifen benzyl Isocycloseram
Cyhalofop butyl Bentazone Chlorantraniliprole
Cyhalofop butyl Bentazone Cyantraniliprole
Cyhalofop butyl Bentazone Cyclaniliprole
Cyhalofop butyl Bentazone Tetraniliprole
Cyhalofop butyl Bentazone Broflanilide
Cyhalofop butyl Bentazone Isocycloseram
Cyhalofop butyl Carfentrazone ethyl Chlorantraniliprole
Cyhalofop butyl Carfentrazone ethyl Cyantraniliprole
Cyhalofop butyl Carfentrazone ethyl Cyclaniliprole
Cyhalofop butyl Carfentrazone ethyl Tetraniliprole
Cyhalofop butyl Carfentrazone ethyl Broflanilide
Cyhalofop butyl Carfentrazone ethyl Isocycloseram
Cyhalofop butyl Sulfentrazone Chlorantraniliprole
Cyhalofop butyl Sulfentrazone Cyantraniliprole
Cyhalofop butyl Sulfentrazone Cyclaniliprole
Cyhalofop butyl Sulfentrazone Tetraniliprole
Cyhalofop butyl Sulfentrazone Broflanilide
Cyhalofop butyl Sulfentrazone Isocycloseram
Cyhalofop butyl Saflufenacil Chlorantraniliprole
Cyhalofop butyl Saflufenacil Cyantraniliprole
Cyhalofop butyl Saflufenacil Cyclaniliprole
Cyhalofop butyl Saflufenacil Tetraniliprole
Cyhalofop butyl Saflufenacil Broflanilide
Cyhalofop butyl Saflufenacil Isocycloseram
Cyhalofop butyl Tetflupyrolimet Chlorantraniliprole
Cyhalofop butyl Tetflupyrolimet Cyantraniliprole
Cyhalofop butyl Tetflupyrolimet Cyclaniliprole
Cyhalofop butyl Tetflupyrolimet Tetraniliprole
Cyhalofop butyl Tetflupyrolimet Broflanilide
Cyhalofop butyl Tetflupyrolimet Isocycloseram
Cyhalofop butyl Cyclopyrimorate Chlorantraniliprole
Cyhalofop butyl Cyclopyrimorate Cyantraniliprole
Cyhalofop butyl Cyclopyrimorate Cyclaniliprole
Cyhalofop butyl Cyclopyrimorate Tetraniliprole
Cyhalofop butyl Cyclopyrimorate Broflanilide
Cyhalofop butyl Cyclopyrimorate Isocycloseram
Cyhalofop butyl Ipfencarbazone Chlorantraniliprole
Cyhalofop butyl Ipfencarbazone Cyantraniliprole
Cyhalofop butyl Ipfencarbazone Cyclaniliprole
Cyhalofop butyl Ipfencarbazone Tetraniliprole
Cyhalofop butyl Ipfencarbazone Broflanilide
Cyhalofop butyl Ipfencarbazone Isocycloseram
Cyhalofop butyl Fenoxasulfone Chlorantraniliprole
Cyhalofop butyl Fenoxasulfone Cyantraniliprole
Cyhalofop butyl Fenoxasulfone Cyclaniliprole
Cyhalofop butyl Fenoxasulfone Tetraniliprole
Cyhalofop butyl Fenoxasulfone Broflanilide
Cyhalofop butyl Fenoxasulfone Isocycloseram
Cyhalofop butyl Pyroxasulfone Chlorantraniliprole
Cyhalofop butyl Pyroxasulfone Cyantraniliprole
Cyhalofop butyl Pyroxasulfone Cyclaniliprole
Cyhalofop butyl Pyroxasulfone Tetraniliprole
Cyhalofop butyl Pyroxasulfone Broflanilide
Cyhalofop butyl Pyroxasulfone Isocycloseram
Cyhalofop butyl Tefuryltrione Chlorantraniliprole
Cyhalofop butyl Tefuryltrione Cyantraniliprole
Cyhalofop butyl Tefuryltrione Cyclaniliprole
Cyhalofop butyl Tefuryltrione Tetraniliprole
Cyhalofop butyl Tefuryltrione Broflanilide
Cyhalofop butyl Tefuryltrione Isocycloseram
Cyhalofop butyl Tefuryltrione Chlorantraniliprole
Cyhalofop butyl Fenquinotrione Cyantraniliprole
Cyhalofop butyl Fenquinotrione Cyclaniliprole
Cyhalofop butyl Fenquinotrione Tetraniliprole
Cyhalofop butyl Fenquinotrione Broflanilide
Cyhalofop butyl Fenquinotrione Isocycloseram
Cyhalofop butyl Lancotrione sodium Chlorantraniliprole
Cyhalofop butyl Lancotrione sodium Cyantraniliprole
Cyhalofop butyl Lancotrione sodium Cyclaniliprole
Cyhalofop butyl Lancotrione sodium Tetraniliprole
Cyhalofop butyl Lancotrione sodium Broflanilide
Cyhalofop butyl Lancotrione sodium Isocycloseram
Cyhalofop butyl Tiafenacil Chlorantraniliprole
Cyhalofop butyl Tiafenacil Cyantraniliprole
Cyhalofop butyl Tiafenacil Cyclaniliprole
Cyhalofop butyl Tiafenacil Tetraniliprole
Cyhalofop butyl Tiafenacil Broflanilide
Cyhalofop butyl Tiafenacil Isocycloseram
Cyhalofop butyl Cyclopyranil Chlorantraniliprole
Cyhalofop butyl Cyclopyranil Cyantraniliprole
Cyhalofop butyl Cyclopyranil Cyclaniliprole
Cyhalofop butyl Cyclopyranil Tetraniliprole
Cyhalofop butyl Cyclopyranil Broflanilide
Cyhalofop butyl Cyclopyranil Isocycloseram
Metamifop 2,4-D Chlorantraniliprole
Metamifop 2,4-D Cyantraniliprole
Metamifop 2,4-D Cyclaniliprole
Metamifop 2,4-D Tetraniliprole
Metamifop 2,4-D Broflanilide
Metamifop 2,4-D Isocycloseram
Cyhalofop butyl 2,4-D Chlorantraniliprole
Cyhalofop butyl 2,4-D Cyantraniliprole
Cyhalofop butyl 2,4-D Cyclaniliprole
Cyhalofop butyl 2,4-D Tetraniliprole
Cyhalofop butyl 2,4-D Broflanilide
Cyhalofop butyl 2,4-D Isocycloseram
Metamifop Bispyribac sodium+Bentazon Chlorantraniliprole
Metamifop Bispyribac sodium+Bentazon Cyantraniliprole
Metamifop Bispyribac sodium+Bentazon Broflanilide
Metamifop Bispyribac sodium+Bentazon Tetraniliprole
Metamifop Bispyribac sodium+Carfentrazone ethyl Chlorantraniliprole
Metamifop Bispyribac sodium+Carfentrazone ethyl Cyantraniliprole
Metamifop Bispyribac sodium+Carfentrazone ethyl Broflanilide
Metamifop Bispyribac sodium+Carfentrazone ethyl Tetraniliprole
Metamifop Florpyrauxifen benzyl+Carfentrzone ethyl Chlorantraniliprole
Metamifop Florpyrauxifen benzyl+Carfentrzone ethyl Cyantraniliprole
Metamifop Florpyrauxifen benzyl+Carfentrzone ethyl Broflanilide
Metamifop Florpyrauxifen benzyl+Carfentrzone ethyl Tetraniliprole
Metamifop Florpyrauxifen benzyl+Bentazon Chlorantraniliprole
Metamifop Florpyrauxifen benzyl+Bentazon Cyantraniliprole
Metamifop Florpyrauxifen benzyl+Bentazon Broflanilide
Metamifop Florpyrauxifen benzyl+Bentazon Tetraniliprole
Clodinafop Propargyl Propaquizafop+Fomesafen Chlorantraniliprole
Clodinafop Propargyl Propaquizafop+Fomesafen Cyantraniliprole
Clodinafop Propargyl Propaquizafop+Fomesafen Broflanilide
Clodinafop Propargyl Propaquizafop+Fomesafen Tetraniliprole
Clodinafop Propargyl Quizalofop-P-Ethyl+Acifluorfen Chlorantraniliprole
Clodinafop Propargyl Quizalofop-P-Ethyl+Acifluorfen Cyantraniliprole
Clodinafop Propargyl Quizalofop-P-Ethyl+Acifluorfen Broflanilide
Clodinafop Propargyl Quizalofop-P-Ethyl+Acifluorfen Tetraniliprole

The herbicidal herbicidal combination of the present invention maybe used to control the target weeds among the crops such as GMO (Genetically Modified Organism) and Non GMO varieties of Cotton (Gossypium spp.), Paddy (Oryza sativa), Wheat (Triticum aestavum), Barley (Hordeum vulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Oat (Avena sativa), Pearl millet (Pennisetum glaucum), Sugarcane (Saccharum officinarum), Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Green gram (Vigna radiata), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun) , Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold (Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Gerbera (Gerbera jamesonii), Carnation (Dianthus caryophyllus).
The present invention of synergistic herbicidal combinations can be also used to control unwanted vegetation in plantation crops, orchards, fallow lands, water bodies, field bunds etc.
A herbicidal synergistic composition of present invention controls all kind of monocots, dicots and sedges weeds. The present synergistic herbicidal combinations also controls annual and perennial weeds. The most common weeds controlled by present inventions are Abutilon indicum, Acalypha indica, Acanthospermum hispidum, Achyranthes aspera, Aerva tomentosa, Ageratum conyzoides, Alhagi camelorum, Amaranthus hybridus, Amaranthus spinosus, Amaranthus viridis, Ammannia baccifera, Anagallis arvensis, Argemone mexicana, Artemisia nilagiricia, Asphodelus tenuifolius, Avena fatua, Avena ludoviciana, Bidens pilosa, Boerhaavia diffusa, Boerhavia repanda, Brachiaria mutica, Brassica kaber, Bromus tectorum, Calotropis gigantea, Cannabis sativa, Carthamus axyacantha, Cassia tora, Celosia argentea, Centella asiatica, Chenopodium album, Chenopodium murale, Chloris barbata, Chrozophora rottlerii, Cichorium intybus, Cirsium arvense, Clitoria ternatea, Cnicus arvensis, Commelina benghalensis, Commelina communis, Convolvulus arvensis, Conyza canadensis, Corchorus acutangulus, Coronopus didymus, Crotalaria serice, Cucumis callosus, Cuscuta campestris, Cuscuta chinensis, Cynodon dactylon, Cyanotis axillaris, Cyperus esculenthus, Cyperus iria, Cyperus rotundus, Dactyloctenium aegyptium, Datura stramonium, Daucus carota, Digera arvensis, Digitaria sanguinalis, Dinebra retroflexa, Echinochola colonum, Echinochola crusgalli, Eclipta alba, Eichhornia crassipes, Elephantopus scaber, Eleusine indica, Eragrostis major, Euphorbia geniculata, Euphorbia hirta, Fimbristylis miliacea, Fumaria indica, Gynandropsis gynandra, Heliotropium indicum, Indigofera glandulosa, Ipomea aquatica, Lantana camara, Lathyrus aphaca, Launaea asplenifolia, Launaea nudicaulis, Leucas aspera, Ludwigia parviflora, Marsilea quadrifoliata, Medicago denticulate, Mimosa pudica, Melilotus alba, Melilotus indica, Ocimum canum, Oenothera biennis, Opuntia dillenil, Orobanche ramosa, Oryza longistaminata, Oryza sativa, Oxalis corniculata, Oxalis latifolia, Parthenium hysterophorus, Paspalum sanguinale, Phalaris minor, Phyllanthus niruri, Physalis minima, Polypogon monspeliensis, Portulaca oleracea, Prosopis juliflora, Rumex dentatus, Saccharum spontaneum, Stearia glauca, Seteria viridis, Sida spinosa, Silene antirrhina, Sisymbrium irio, Solanum nigrum, Solanum surattense, Sonchus oleraceous, Sorghum halepense, Spergula arvensis, Sphenocleazeylanica Gaertn, Striga asiatica, Tagetes minuta, Trianthema monogyna, Trianthema portulacastrum, Tribulus terrestris, Trigonelia polycerata, Vernonia cinerea, Vicia sativa and Xanthium strumarium.
Formulation of the present invention can be in any of the formulations selected from Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion, oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule (GR) / Soil Applied Granules (SAG), Controlled release granules (CR).
Further formulation for the present synergistic agrochemical composition comprises ‘crop safener’ for use especially in monocotyledonous crops (wheat, paddy/rice, corn/maize, sugarcane, sorghum, pearlmillet).
In an embodiment of the present invention any one of the crop safener for the monocotyledonous (example-rice, wheat, barley, maize, sorghum, pearlmillet, sugarcane etc.) crops is selected from the cyprosulfamide, dietholate, isoxadifen / isoxadifen ethyl, dicyclonon, benoxacor, mefenpyr ethyl, fenchlorazole ethyl, cloquintocet / cloquintocet mexyl, oxabetrinil, naphthalic anhydride, mephenate, mefenpyr, furilazole, fluxofenim, flurazole, fenclorim, fenchlorazole, dichlormid or cyometrinil.
One or more of the active ingredients is encapsulated for various purposes, such as to increase the residual biological activity, or to reduce the acute toxicity, or to obtain a physical or chemically stable water-based formulation. The purpose determines whether the “free” active ingredient and the “release rate” are relevant properties of a specific product.
Further herbicidal composition comprising (A) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor for control of grasses or mixture thereof; (B) a one or more herbicide(s) selected from the group of various class of compounds for control of broad-leaved weeds and grasses in crops of useful plants or mixture thereof; and (C) an insecticide selected from the class of diamide, metadiamide or isoxazoline as safener for reducing phytotoxicity in crops on post herbicide application or mixture thereof; are present in the said composition in specific fixed ratio.
In further aspect the present invention relates to the synergistic herbicidal composition comprising bioactive amounts of (A) is 0.1 to 60% w/w of the composition; (B) is 0.001 to 60% w/w of the composition; and (C) is 0.001 to 30% w/w of the composition.
Active Ingredients Compound A Compound B Compound C

Examples Acetyl CoA Carboxylase (ACCase) Inhibitor One or more herbicide(s) Insecticide as safener from the class of diamide, metadiamide or isoxazolines
% of Active Ingredient (w/w, w/v)
0.1 to 60%
0.001 to 60%
0.001 to 30%
The composition of the present invention in addition to bioactive amounts of active ingredients further comprises inactive excipients including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, antimicrobial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.
A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. Examples of such agents used herein Oil Dispersion, Suspension Concentrate and Suspo Emulsion formulations include, but are not limited to Methylnaphthalene sulfonic acid -formaldehyde polymer sodium salt, Methyl oxirane, block copolymer, Methyl naphthalenes, Alkylaryl sulfonate, Acrylic copolymer blend, alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium ploycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, Acrylic graft copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, Polyarylphenyl ether sulphate ammonium salt oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide.
Anti-freezing agent as used herein can be selected from the group consisting of polyethylene glycols, methoxy polyethylene glycols, dipropylene glycol, polypropylene glycols, propylene glycol, polybutylene glycols, glycerine, ethylene glycol, Urea.
Water-based formulations often cause foam during mixing operations in production. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Antifoaming agents as used herein can be selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethylsiloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane.
A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in Micro Emulsion, Oil Dispersion, suspension concentrate, Emulsifiable Concentrate and Suspo Emulsion formulations include but not limited to Ethoxylated alcohol, Alkylphenol alkoxylate, ethylene oxide/propylene oxide block copolymer, polyarylphenyl ether phosphate, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyldiphenyl sulfonates, Octyl phenol ethoxylate, alkyl phenol ethoxylate, sodium isopropyl naphthalene sulfonate, alkylnaphthalene sulfonate, organosilicons surfactants (as a wetting-spreading-penetrating agent) includes trisiloxane ethoxylate, Blend of alcohol ethoxylate and alkyl phenol ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, Ethoxylated tridecyl and/ or isotridecyl alcohol, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, may or may not be in modified form, may be liquid or powder form or mixture thereof etc.
Examples of emulsifying agents as used herein Emulsifiable Concentrate and Micro-Emulsion formulation include salts of dodecylbenzene sulphonate, e.g. Ca-salts or amine salts, and sulphonates of other C11-C16 alkylbenzenes, alkylether sulphates, alkylphenoletherphosphates and ester phosphates; non-ionic surfactants such as alkoxylated alcohols and alkylphenols, ethoxylated fatty acids, ethoxylated vegetable oils, e.g. ethoxylated castor oil, fatty acid esters, e.g. of sorbitol, and their ethoxylated derivatives, ethoxylated amines, and condensates of glycerol; and catanionic emulsifiers such as a cationic amine, optionally in combination with an alkylsulphonate or ether sulphonate or ether phosphate, alkoxylated alcohols; alkoxylated alkylphenols; ethoxylated fatty acids; ethoxylated vegetable oils; ethoxylated tristyrylphenol; fatty acid esters of sorbitol and ethoxylated derivatives thereof; ethoxylated amines and condensates of glycerol; sulfonated alkylbenzenes in the range C11-C16 and salts thereof; alkylether sulphates; alkyletherphosphates; alkylphenoletherphosphates; or combinations thereof; salts of phosphate esters of ethoxylated tristyrylphenol; salts of sulphated ethers of ethoxylated tristyrylphenol; or a catanionic system, wherein a cationic amine is present in combination with an alkylsulphonate, an alkylethersulphonate, an ether sulphate, or an ether phosphate such as an alkyletherphosphate, Polysorbate 20, nonylphenol polyethoxy ethanols, castor oil polyglycol ethers, polyadducts of ethylene oxide and polypropylene, tributyl phenoxy polyethoxy ethanol, octyl phenoxy polyethoxy ethanol.
Suspension aid in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being applied to. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof).
Stabilizer as used herein Suspo Emulsion formulation can be selected from bentonite clay, butylated hydroxytoluene (BHT) and epoxidized soybean oil (ESBO), Epichlorhydrin.
Biocides / Microorganisms cause spoilage of formulated products. Therefore antimicrobial agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: 1,2-benzisothiazolin-3(2H)-one, 1,2-benzisothazol-3-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, formaldehyde, sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one, Lactic acid.
Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, e.g. bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof. Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.
Buffering agent as used herein is selected from group consisting of EDTA-4NA, calcium hydroxyapatite, Acetic acid glacial, Potassium Dihydrogen Phosphate, Oleic acid, Citric acid, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase, Ammonium hydroxide and magnesium hydroxide.
The solvent for the formulations of the present invention may include water, water soluble alcohols and dihydroxy alcohol ethers, Solvent naphta (petrolium) heavy aromatic, Mixed xylene, Cyclohexanone, vegetable oil (plant, seed or tree) or its alkylated or ethoxylated or esterified. The alkylated vegetable oil may be methylated vegetable oil or ethylated vegetable oil. The vegetable oils include olive oil, kapok oil, castor oil, papaya oil, camellia oil, sesame oil, corn oil, rice bran oil, cotton seed oil, soybean oil, groundnut oil, rapeseed-mustard oil, linseed oil, tung oil, sunflower oil, safflower oil, coconut oil. The alkyl ester of vegetable oils includes methyl ester, ethyl ester, propyl ester or butyl ester of vegetable oils. Some of the examples are Methylated seed oil, polyalkyleneoxide modified polydimethylsiloxane alkylphenol ethoxylate, rapeseed oil methyl ester, rapeseed oil ethyl ester, rapeseed oil propyl esters, rapeseed oil butyl esters, soybean oil methyl ester, soybean oil ethyl ester, soybean oil propyl ester, soybean oil butyl ester, castor oil methyl ester, castor oil ethyl ester, castor oil propyl ester, castor oil butyl ester, cotton seed oil methyl ester, cotton seed oil ethyl ester, cotton seed oil butyl ester, cotton seed oil propyl ester, tall oil fatty acids esters-tallow methyl ester, tallow ethyl ester, tallow propyl ester, bio-diesel, mineral oil (aromatic solvents, isoparaffin, base solvent), fatty acid amides (e.g. C1 -C3 amines, alkylamines or alkanolamines with C6–C18 carboxylic acids), fatty acids, alkyl esters of fatty acids, methyl and ethyl oleate, methyl and ethyl soyate, alkyl benzenes and alkylnaphthalenes, polyalkylene glycol ethers, fatty acid diesters, fatty alkylamides and diamides, dialkylene carbonates, ketones and alcohols. The above oil based carrier/diluting agents may be used as solo or mixture of two or more if desired.
The process for preparing the present novel synergistic composition can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.
These and other aspects of the invention may become more apparent from the examples set forth herein below. These examples are provided merely as illustrations of the invention and are not intended to be construed as a limitation thereof.
EXAMPLE 1:
ME (Micro-emulsion) Formulation of Propaquizafop 2.5%+Imazethapyr 3.75%+Chlorantraniliprole 1.5%
Chemical composition % (w/w)
Propaquizafop a.i. 2.50
Imazethapyr a.i. 3.75
Chlorantraniliprole a.i. 1.50
Ammonium hydroxide 1.30
Ethoxylated alcohol 13.90
EDTA-4NA 0.03
Acetic acid glacial 0.04
Urea 2.17
Polydimethyl siloxane 0.01
Lactic acid 0.09
Polysorbate 20 27.80
Dipropylene glycol 9.26
Propylene glycol 21.25
Methyl naphthalenes 7.67
Water 8.73
Total 100.00

Procedure: Manufacturing process of ME (Micro-emulsion) Formulation
Preparation of ME (Micro-emulsion) formulation:
Step 1 Charge required quantity of solvent & cosolvent and then mix the technical into this solvent untill completely soluble.
Step 2 Now add required surfactants as per their dose in recipe
Step 3 Now add remaining solvent to this mixture
Step 4 Final product is sent for QC approval.
Step 5 After approval material is packed in requied pack sizes.

Storage stability-
Propaquizafop 2.5%+Imazethapyr 3.75%+Chlorantraniliprole 1.5% ME
Storage stability study in laboratory (at 54±2 C & At 0±2 C temp. for 14 days) and at room temperature (for 12 months) shows that Propaquizafop 2.5%+Imazethapyr 3.75%+Chlorantraniliprole 1.5% ME formulation complies all the in-house parameters like active ingredients content, suspensibility, pH range, pourability, specific gravity, viscosity, particle size and anti-foaming.
Following table provides more examples of combinations and formulation of Micro-Emulsion prepared as per EXAMPLE 1
Compound A (%) Compound B (%) Compound C (%) Formulation Strength (%)
EXAMPLE 2 Propaquizafop 2.5% Imazethapyr 3.75% Chlorantraniliprole 1.5% 7.75
EXAMPLE 3 Propaquizafop 2.5% Imazethapyr 3.75% Broflanilide 0.6% 6.85

EXAMPLE 4:
OD (Oil dispersion) formulation of Cyhalofop-butyl 5%+Penoxsulam 1%+Chlorantraniliprole 1.5%
Chemical composition % (w/w)
Cyhalofop butyl a.i. 5.10
Penoxsulam a.i. 1.02
Chlorantraniliprole a.i. 1.50
Propylene glycol 0.06
Methylnaphthalene sulfonic acid -formaldehyde polymer sodium salt 0.08
Methyl oxirane, block copolymer 0.02
Alkylphenol alkoxylate 38.50
Polydimethylsiloxane 0.001
1,2-benzisothiazolin-3(2H)-one 0.0004
Alkylaryl sulfonate 1.85
Oleic acid 0.57
Citric acid 0.004
Methyl soyate 27.60
Silica dimethyl silyate 2.28
Silicon dioxide 0.46
Acrylic copolymer blend 0.23
Cellulose 0.002
Xanthum gum 0.002
Water 0.83
Solvent naphta (petrolium) heavy aromatic 19.89
Total 100.00

Procedure: Manufacturing process of OD (Oil dispersion) formulation
Preparation of Oil dispersion (OD) formulation:
Part A Preparation of the liquid premix
Step 1 Charge Vegetable oil or solvent or both into a vessel with anchor stirrer.
Step 2 Under stirring, add the emulsifier and dispersing agent and stir until all ingredients are dissolved completely.
Part B Preparation of the slurry
Step 1 Now, charge the liquid premix into a second vessel, equipped with a cooling and heating device and a high shear stirrer.
Step 2 Add the active ingredient and homogenize thoroughly. Pre-mill this mixture and finally mill it using a bead mill to achieve a particle size distribution as required by the specification.
Part C Preparation of the Thickener gel
Step 1 Charge the vegetable/plant/seed oil or solvent to the vessel, equipped with a high shear stirrer.
Step 2 Add gradually the thickener which is organophilic clay, maintaining high-shear mixing throughout. Stirring is continued until thoroughly mixed.
Step 3 Under stirring, the thickener activating agent is added. Allow the gel to swell whilst maintaining mixing.
Part D Preparation of the final formulation
Step 1 Now add the thickener gel or silica and disperse the mixture by using a high shear stirrer.
Step 2 Finally add the recommended wetting and spreading agent or adjuvants (silicone or non-silicone based) to this formulation and disperse by using high shear stirrer.
Step 3 Check the finished formulation to specification.
Step 4 After approval, material is packed in required pack sizes.

Storage stability-
Cyhalofop-butyl 5%+Penoxsulam 1%+Chlorantraniliprole 1.5% OD
Storage stability study in laboratory (at 54±2 C & At 0±2 C temp. for 14 days) and at room temperature (for 12 months) shows that Cyhalofop-butyl 5%+Penoxsulam 1%+Chlorantraniliprole 1.5% OD formulation complies all the in-house parameters like active ingredients content, suspensibility, pH range, pourability, specific gravity, viscosity, particle size and anti-foaming.

Following table provides more examples of preferred combinations and formulation of Oil Dispersion prepared as per EXAMPLE 4.
Compound A (%) Compound B (%) Compound C (%) Formulation Strength (%)
EXAMPLE 5 Cyhalofop-butyl 5% Penoxsulam 1% Chlorantraniliprole 1.5% 7.50
EXAMPLE 6 Cyhalofop butyl 6% Tefuryltrione 4% Chlorantraniliprole 3% 13.00
EXAMPLE 7 Cyhalofop butyl 6% Fenquinotrione 10% Chlorantraniliprole 3% 19.00
EXAMPLE 8 Cyhalofop butyl 6% Lancotrion sodium 10% Chlorantraniliprole 3% 19.00
EXAMPLE 9 Cyhalofop butyl 6% Cyclopyrimorate 15% Chlorantraniliprole 3% 24.00
EXAMPLE 10 Cyhalofop butyl 6% Tetflupyrolimet 15% Chlorantraniliprole 3% 24.00
EXAMPLE 11 Cyhalofop butyl 3% Bentazone 30% Chlorantraniliprole 3% 36.00

EXAMPLE 12:
SE (Suspo emulsion) Formulation of Metamifop 3%+Bentazone 30%+Tetraniliprole 2%
Chemical composition % (w/w)
Metamifop a.i. Active ingredient 3.00
Bentazone a.i. Active ingredient 30.00
Tetraniliprole a.i. Active ingredient 2.00
Octyl phenol Ethoxylate Solvent 10.00
Trisiloxane ethoxylate Wetting-spreading-penetrating agent 5.00
Tristyrylphenol-polyglycolether-phosphate Dispersing agent 1 4.50
Polyarylphenyl ether sulphate ammonium salt Dispersing agent 2 1.00
Bentonite clay Suspending agent 2.00
Polydiemthylsiloxane Antifoaming agent 0.30
2-bromo-2-nitropropane-1,3-diol Preservative 0.20
Polypropylene glycol Antifreezing agent 5.00
Xanthan gum Thickner 0.15
Water Diluent Water 36.85
Total 100.00

Procedure: Manufacturing process of SE (Suspo emulsion) formulation
Preparation of Suspo Emulsion (SE) formulation:
Step 1 2% Gel Preparation: Charge the required quantity of water to a vessel, equipped with a high shear stirrer and start the agitation. Add the required amount of preservative. Mix until homogenous. Add the required amount of thickener and mix vigorously until it is fully wetted.
Step 2 Oil Phase: Charge solvent into the vessel and then add active technical slowly and if required, heat it for 50? so that technical can be dissolved in solvent and then add emulsifier.
Step 3 Charge the required quantity of water to a vessel, equipped with bulk agitator and a high shear homogenizer and start agitation. Add the required amount of ant freezing agent and mix until uniform. Add the antifoaming agent and ensure that it is well dispersed. Add the wetting and dispersing agent and mix until uniform. Ensure that the dispersing agent is fully dispersed.
Step 4 Now add the active ingredient and continue agitating the vessel contents until all components get dissolved. Mill this pre-mix through a Colloid mill and subsequently through a Dyno mill to meet the specified particle size.
Step 5 Now add remaining antifoaming agent to this mill base to a vessel, equipped with bulk agitator. Mix until uniform.
Step 6 Now add oil phase in aqueous phase and stir for 30 minutes using homogenizer.
Step 7 Add the required amount of 2% aqueous pre-gel and also suspending agent and continue agitation until the formulation is homogeneous and has the target viscosity. Mix well.
Step 8 Final product is sent for QC approval.
Step 9 After approval, material is packed in required pack sizes.

Storage stability-
Metamifop 3%+Bentazone 30%+Tetraniliprole 2% SE
Storage stability study in laboratory (at 54±2 C & At 0±2 C temp. for 14 days) and at room temperature (for 12 months) shows that Metamifop 3%+Bentazone 30%+Tetraniliprole 2% SE (Suspo emulsion) formulation complies all the in-house parameters like active ingredients content, suspensibility, pH range, pourability, specific gravity, viscosity, particle size and anti-foaming.

Following table provides more examples of preferred combinations and formulation of Suspo Emulsion prepared as per EXAMPLE 12.
Compound A (%) Compound B (%) Compound C (%) Formulation Strength (%)
EXAMPLE 13 Metamifop 6% Tefuryltrione 4% Tetraniliprole 4% 14.00
EXAMPLE 14 Metamifop 6% Fenquinotrione 10% Tetraniliprole 4% 20.00
EXAMPLE 15 Metamifop 6% Lancotrion sodium 10% Tetraniliprole 4% 20.00
EXAMPLE 16 Metamifop 6% Cyclopyrimorate 15
% Tetraniliprole 4% 25.00
EXAMPLE 17 Metamifop 6% Tetflupyrolimet 15% Tetraniliprole 4% 25.00
EXAMPLE 18 Metamifop 3% Bentazone 30% Tetraniliprole 2% 35.00
EXAMPLE 19 Metamifop 7.5% Bispyribac sodium 2% Cyantraniliprole 6% 15.50

EXAMPLE 20:
SC (Suspension Concentrate) Formulation of Quizalofop ethyl 3%+Fomesafen 12%+Chlorantraniliprole 2%
Chemical composition % (w/w)
Quizalofop ethyl a.i. Active ingredient 3.00
Fomesafen a.i. Active ingredient 12.00
Chlorantraniliprole a.i. Active ingredient 1.50
Trisiloxane ethoxylate Wetting-spreading-penetrating agent 5.00
Acrylic graft copolymer Dispersing agent 1 4.50
Ethoxylated tridecyl and/ or isotridecyl alcohol Dispersing agent 2 1.50
Attapulgite clay Suspending agent 0.50
Polydimethyl siloxane Antifoaming agent 0.20
1,2-benzisothazol-3-one Preservative 0.15
Polypropylene glycol Antifreezing agent 5.00
Xanthan gum Thickner 0.20
Water Water 66.45
Total 100.00

Procedure: Manufacturing process of SC (Suspension Concentrate) Formulation
Preparation of Suspension Concentrate (SC) formulation:
Step 1 2% Gel Preparation: Charge the required quantity of water to a vessel, equipped with a high shear stirrer and start the agitation. Add the required amount of preservative. Mix until homogenous. Add the required amount of thickener and mix vigorously until it is fully wetted.
Step 2 Charge the required quantity of water to a vessel, equipped with bulk agitator and a high shear homogenizer and start agitation. Add the required amount of ant freezing agent and mix until uniform. Add the antifoaming agent and ensure that it is well dispersed. Add the wetting and dispersing agent and mix until uniform. Ensure that the dispersing agent is fully dispersed.
Step 3 Now add the active ingredient and continue agitating the vessel contents until all components get dissolved. Mill this pre-mix through a Colloid mill and subsequently through a Dyno mill to meet the specified particle size.
Step 4 Now add remaining antifoaming agent to this SC mill base to a vessel, equipped with bulk agitator. Mix until uniform. Add the required amount of 2% aqueous pre-gel and suspending agent and continue agitation until the formulation is homogeneous and has the target viscosity is reached.
Step 5 Final product is sent for QC approval.
Step 6 After approval, material is packed in required pack sizes.

Storage Stability-
Quizalofop ethyl 3%+Fomesafen 12%+Chlorantraniliprole 2% SC
Storage stability study in laboratory (at 54±2 C & At 0±2 C temp. for 14 days) and at room temperature (for 12 months) shows that Quizalofop ethyl 3%+Fomesafen 12%+Chlorantraniliprole 2% SC formulation complies all the in-house parameters like active ingredients content, suspensibility, pH range, pourability, specific gravity, viscosity, particle size and anti-foaming.

Following table provides more examples of preferred combinations and formulation of Suspension Concentrate prepared as per EXAMPLE 20.
Compound A (%) Compound B (%) Compound C (%) Formulation Strength (%)
EXAMPLE 21 Quizalofop ethyl 3% Fomesafen 12% Chlorantraniliprole 2% 17.00
EXAMPLE 22 Quizalofop ethyl 3% Fomesafen 12% Broflanilide 0.8% 15.80
EXAMPLE 23 Haloxyfop R methyl 8% Chlorimuron ethyl 0.9% Chlorantraniliprole 3% 11.90

EXAMPLE 24:
EC (Emulsifiable concentrate) Formulation of Clodinafop Propargyl 8%+Acifluorfen 16.5%+Broflanilide 1.2%
Chemical composition % (w/w)
Clodinafop propargyl a.i. Active ingredient 8.00
Acifluorfen a.i Active ingredient 16.50
Broflanilide a.i. Active ingredient 1.20
Blend of alcohol ethoxylate and alkyl phenol ethoxylate Wetting agent 18.25
Calcium dodecyl benzene sulphonate Emulsifier 0.75
Mixed xylene Solvent 16.00
Cyclohexanone Solvent 39.30
Total 100.00

Procedure: Manufacturing process of EC (Emulsifiable concentrate) Formulation
Preparation of EC (Emulsifiable concentrate) formulation:
Step 1 Charge required quantity of solvent and then mix the technical into this solvent untill completely soluble.
Step 2 Now add surfactants dose as per screening ration.
Step 3 Now add remaining solvent to this mixture.
Step 4 Final product is sent for QC approval.
Step 5 After approval material is packed in requied pack sizes.

Storage stability-
Storage stability study in laboratory (at 54±2 C & At 0±2 C temp. for 14 days) and at room temperature (for 12 months) shows that Clodinafop Propargyl 8%+Acifluorfen 16.5%+Broflanilide 1.2% EC formulation complies all the in-house parameters like active ingredients content, pH range, specific gravity, viscosity and particle size.

Following table provides more examples of preferred combinations and formulation of Emulsifiable concentrate prepared as per EXAMPLE 24.
Compound A (%) Compound B (%) Compound C (%) Formulation Strength (%)
EXAMPLE 25 Clodinafop Propargyl 8% Acifluorfen 16.5% Chlorantraniliprole 3% 14.00
EXAMPLE 26 Propaquizafop 5% Oxyfluorfen 12% Chlorantraniliprole 3.4% 20.40
EXAMPLE 27 Clodinafop Propargyl 8% Acifluorfen 16.5% Broflanilide 1.2% 25.70
EXAMPLE 28 Propaquizafop 5% Oxyfluorfen 12% Broflanilide 1.33 18.33
EXAMPLE 29 Haloxyfop R methyl 8% Imazethapyr 7% Chlorantraniliprole 3% 18.00
EXAMPLE 30 Haloxyfop R methyl 8% Imazamox 7% Chlorantraniliprole 3% 18.00
EXAMPLE 31 Haloxyfop R methyl 8% Acifluorfen sodium 16.5% Chlorantraniliprole 3% 27.50
EXAMPLE 32 Haloxyfop R methyl 8% Fomesafen sodium 18% Chlorantraniliprole 3% 29.00
EXAMPLE 33 Haloxyfop R methyl 8% Lactofen 18% Chlorantraniliprole 3% 29.00
EXAMPLE 34 Haloxyfop R methyl 8% Fluthiacet methyl 1.35% Chlorantraniliprole 3% 12.35

Biological Examples:
The field experiments were carried out to judge the impact of insecticide (diamide, Metadiamides and Isoxazoline) on crop safety and yield when applied with herbicidal compositions (Acetyl CoA Carboxylase-ACCase Inhibitor + one or more herbicides) as inbuilt formulation and tank mixes.

EXAMPLE 35: Crop safety and weed control in soybean, Glycine max
Crops: Soybean
No. of Treatments: As per treatment details
Plot size: 25 sq. mt.
Application Time: 15 DAS (Days after sowing)
Spray Volume: 375 liter water per hectare
Application Equipment: Manually operated knapsack sprayer fitted with flat fat nozzle
Agronomic practices: All the required agronomic practices followed except herbicidal application.
Observations:
Phytotoxicity: The observations on crop safety i.e. phytotoxicity or adverse effect of treatments were recorded on 7th 14th and 21st DAA (days after application). All the visual phytotoxicity symptoms like plant yellowing, leaf scorching, bleaching, necrosis, stunting, crinkling, epinasty, hyponasty recorded on the basis of entire plot in comparison with untreated control (UTC) plot. Each individual visual symptoms were recorded on the basis severity of injury i.e. from 0 to 100%.
Weed control: Weed count were recorded at 14 DAA (Days after Application by using (100 cm x 100 cm=1 m2 ) quadrant treatment wise in minimum 4 places randomly selected in the plot. The weed control (%) calculated by using given formula.
The weed control(%) data used in Colby’s formula to calculate the synergism.
A synergistic effect exists wherever the action of a combination of active ingredient is greater than the sum of the action of each of the components alone. Therefore, a synergistically effective amount or an effective amount of a synergistic composition or combination is an amount that exhibits greater pesticidal activity than the sum of the pesticidal activities of the individual components.


Table 1: Treatment details
Treatment number Treatment details Rate (gai/h)
T1 Clodinafop Propargyl 8%+Acifluorfen 16.5%+Chlorantraniliprole 3% EC 80+165+30
T2 Quizalofop ethyl 3%+Fomesafen 12%+Chlorantraniliprole 2% SC 45+180+30
T3 Propaquizafop 2.5%+Imazethapyr 3.75%+Chlorantraniliprole 1.5% ME 50+75+30
T4 Clodinafop Propargyl 8%+Acifluorfen 16.5%+Broflanilide 1.2% EC 80+165+12
T5 Quizalofop ethyl 3%+Fomesafen 12%+Broflanilide 0.8% SC 45+180+12
T6 Propaquizafop 2.5%+Imazethapyr 3.75%+Broflanilide 0.6% ME 50+75+12
T7 Clodinafop Propargyl 8%+Acifluorfen 16.5% EC 80+165
T8 Quizalofop ethyl 3%+Fomesafen 12% SC 45+180
T9 Propaquizafop 2.5%+Imazethapyr 3.75% ME 50+75
T10 Clodinafop Propargyl 15% WP 80
T11 Quizalofop ethyl 10% EC 45
T12 Propaquizafop 10% EC 50
T13 Acifluorfen sodium salt 20% SL+AMS 2g/l+NIS 2 ml/l 165
T14 Fomesafen sodium salt 20% SL+AMS 2g/l+NIS 2 ml/l 180
T15 Imazethapyr 10% SL+AMS 2g/l+NIS 1.5 ml/l 75
T16 Chlorantraniliprole 18.5% SC 30
T17 Broflanilide 30% SC 12
T18 Untreated control (UTC) -

EC Emulsifiable concentrate, SC Suspension concentrate, SL Soluble liquid, WP Wettable powder, ME Micro emulsion, AMS-Ammonium sulphate as spray adjuvant, NIS-Non Ionic Surfactant, g/l gram per liter, ml/l milliliter per liter.
Table 2: Synergistic weed control in soybean
Treatment number Weed control (%) on 14 DAA
Observed Value Calculated Value Colby's ratio Synergism (Y/N)
T1 95.4 78.11 1.22 Y
T2 98.8 80.35 1.23 Y
T3 93.4 79.93 1.17 Y
T4 94.6 78.11 1.21 Y
T5 99.2 80.35 1.23 Y
T6 92.8 79.93 1.16 Y
T7 94.0 78.06 1.20 Y
T8 98.2 80.31 1.22 Y
T9 92.2 79.89 1.15 Y
T10 60.4
T11 63.4
T12 65.8
T13 44.6
T14 46.2
T15 41.2
T16 0.2
T17 0.2
T18 0.0

Weed flora of trial plot: Grassy weeds (Echinochloa colonum, Eragrostis major, Dinebra retroflaxa), Broad leaf weeds (Communila benghalensis, Euphorbia hirta, Acalypha indica, Phyllantus niruri, Sedges (Cyperus rotunds).
All the innovative treatments (T1 to T6) provides synergistic control of weeds in soybean.
Table 3: Phytotoxicity and yield parameters in soybean crop
Treatment number Leaf scorching (%) Yellowing (%) No.of pods per plant Increase(%) in pods over
7 DAA 14 DAA 21 DAA 7 DAA 14 DAA 21 DAA
T1 5.0 0.0 0.0 0.00 0.00 0.00 52.20 12.74 (over T7)
T2 5.0 0.0 0.0 0.00 0.00 0.00 52.70 11.89 (over T8)
T3 0.0 0.0 0.0 5.00 0.00 0.00 51.50 12.69 (over T9)
T4 5.0 0.0 0.0 0.00 0.00 0.00 52.80 14.04 (over T7)
T5 5.0 0.0 0.0 0.00 0.00 0.00 52.00 10.40 (over T8)
T6 0.0 0.0 0.0 5.00 0.00 0.00 51.30 12.25 (over T9)
T7 10.0 5.0 0.0 5.00 0.00 0.00 46.30
T8 10.0 5.0 0.0 5.00 0.00 0.00 47.10
T9 5.0 0.0 0.0 10.00 5.00 0.00 45.70
T10 0.0 0.0 0.0 0.00 0.00 0.00 42.40
T11 0.0 0.0 0.0 0.00 0.00 0.00 41.20
T12 0.0 0.0 0.0 0.00 0.00 0.00 43.20
T13 10.0 5.0 0.0 5.00 0.00 0.00 41.40
T14 10.0 5.0 0.0 5.00 0.00 0.00 41.20
T15 5.0 0.0 0.0 10.00 5.00 0.00 41.00
T16 0.0 0.0 0.0 0.0 0.0 0.0 40.20
T17 0.0 0.0 0.0 0.0 0.0 0.0 40.60
T18 0.0 0.0 0.0 0.0 0.0 0.0 34.60

All the innovative treatments (T1 to T6) shows better crop safety in terms of leaf scorching and yellowing. All the innovative treatments (T1 to T6) produces more number of pods per plant in comparison to conventional treatments (T4, T5 and T6) without insecticides (chlorantraniliprole and broflanilide).

Example 36: Crop safety and weed control in paddy, Oryza sativa
Crops: Paddy/Rice
No. of Treatments: As per treatment details
Plot size: 30 sq. mt.
Application Time: 22 DATP (Days after transplanting)
Spray Volume: 375 liter water per hectare
Application Equipment: Manually operated knapsack sprayer fitted with flat fat nozzle
Agronomic practices: All the required agronomic practices followed except herbicidal application.
Observations:
Phytotoxicity: Recorded on 7, 14 and 21 DAA (as given in Example 1)
Weed control (%): Recorded on 20th DAA (As given in Example 1)
Table 4: Treatment details for crop safety study
Treatment number Treatment details Rate (gai/h)
T1 Cyhalofop-butyl 5%+Penoxsulam 1%+Chlorantraniliprole 1.5% OD 100+20+30
T2 Metamifop 3%+Bentazone 30%+Tetraniliprole 2% SE 60+600+40
T3 Metamifop 7.5%+Bispyribac sodium 2%+Cyantraniliprole 6% SE 75+20+60
T4 Cyhalofop-butyl 10% EC+Penoxsulam 2.67% OD 100+20
T5 Metamifop 10% EC+Bentazone 48% SL 60+600
T6 Metamifop 10% EC+Bispyribac sodium 10% SC 75+20
T7 Cyhalofop-butyl 10% EC+Chlorantraniliprole 18.5% SC 100+30
T8 Metamifop 10% EC+Tetraniliprole 18.81% SC 60+40
T9 Metamifop 10% EC+Cyantraniliprole 10.26% OD 75+60
T10 Penoxsulam 2.67% OD+Chlorantraniliprole 18.5% SC 20+30
T11 Bentazone 48% SL+Tetraniliprole 18.81% SC 600+40
T12 Bispyribac sodium 10% SC+Cyantraniliprole 10.26% OD 20+60
T13 Cyhalofop-butyl 10% EC 100
T14 Metamifop 10% EC 60
T15 Metamifop 10% EC 75
T16 Penoxsulam 2.67% OD 20
T17 Bentazone 48% SL 600
T18 Bispyribac sodium 10% SC 20
T19 Chlorantraniliprole 18.5% SC 30
T20 Tetraniliprole 18.81% SC 40
T21 Cyantraniliprole 10.26% OD 60
T22 Untreated control (UTC) -

Table 5: Synergistic weed control
Treatment number Weed control (%) on 20 DAA
Observed Value Calculated Value Colby's ratio Synergism (Y/N)
T1 96.4 77.96 1.24 Y
T2 94.6 75.73 1.25 Y
T3 92.6 80.70 1.15 Y
T4 96.4 77.92 1.24 Y
T5 94.2 75.68 1.24 Y
T6 92.4 80.66 1.15 Y
T7 61.0 61.48 0.99 N
T8 54.6 54.89 0.99 N
T9 59.8 60.28 0.99 N
T10 42.4 42.91 0.99 N
T11 46.0 46.31 0.99 N
T12 51.0 51.50 0.99 N
T13 61.4
T14 54.8
T15 60.2
T16 42.8
T17 46.2
T18 51.4
T19 0.2
T20 0.2
T21 0.2
T22 0.0

Weed flora of trial plot- Grassy weeds (Echinochloa colonum, Leptochloa chinensis), Broad leaf weeds (Eclipta alba, Alternenthera spp., Sphenochlea spp.), Sedges (Cyprus irria, Cyperus difformis).

All the innovative treatments (T1, T2, T3) provides synergistic control of weeds in rice.
Table 6: Phytotoxicity observations and yield parameters
Treatment number Yellowing (%) Plant height (cm)
45 DAA Productive tillers/m2 Increase(%) in plant height over
7 DAA 14 DAA 21 DAA
T1 5.0 0.0 0.0 102.10 382.80 22.50 (over T4)
T2 5.0 0.0 0.0 101.90 372.60 16.55 (over T5)
T3 5.0 0.0 0.0 101.60 380.40 23.67 (over T6)
T4 10.0 5.0 0.0 98.20 312.50
T5 10.0 5.0 0.0 97.40 319.70
T6 10.0 5.0 0.0 97.80 307.60
T7 5.0 0.0 0.0 98.80 338.20
T8 5.0 0.0 0.0 102.00 330.90
T9 5.0 0.0 0.0 101.80 337.70
T10 5.0 0.0 0.0 101.80 322.80
T11 5.0 0.0 0.0 100.80 325.30
T12 5.0 0.0 0.0 101.20 344.60
T13 0.0 0.0 0.0 99.80 292.40
T14 0.0 0.0 0.0 99.70 286.50
T15 5.0 0.0 0.0 98.60 290.40
T16 5.0 0.0 0.0 97.80 283.90
T17 5.0 0.0 0.0 96.50 276.60
T18 5.0 0.0 0.0 97.30 279.30
T19 0.0 0.0 0.0 98.30 288.60
T20 0.0 0.0 0.0 99.20 280.40
T21 0.0 0.0 0.0 98.60 274.80
T22 0.0 0.0 0.0 95.80 224.40
The innovative treatments (T1,T2, T3) shows very mild yellowing symptoms and recovers very fast and also producing higher number of productive tillers.
Summery of the biological experiments:
• Addition of insecticides (diamide, Metadiamides and Isoxazoline) to shows mild crop injury and crop recovers very fast without loosing potential growth parameters.
• Provides synergistic weed control
• Increases yield attributing parameters

CLAIMS:CLAIMS
We claim;
1) A synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops comprising:
a) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor or mixture thereof in an amount of 0.1 to 60% by weight;
b) one or more herbicide(s) selected from the group of Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor, Synthetic Auxin, Inhibitor of photosynthesis at photosystem II site A, Inhibitor of photosynthesis at photosystem II site B, Inhibitor of lipid synthesis; not ACCase inhibition, Inhibitor of 5-enolypyruvyl-shikimate-3-phosphate synthase (EPSPS), Inhibitor of glutamine synthetase: Phosphonic acid, Inhibitor of phytoene desaturase (PDS), Inhibitor of 1-deoxy-D-xyulose 5-phosphate sunthatase (DOXP synthase), Inhibitor of protoporphyrinogen oxidase (Protox, PPO), Mitosis Inhibitor, Inhibitor of 7,8-dihydro-preroate synthetase (DHP), Inhibitor of indoleacetic acid transport, Inhibitor of cell wall synthesis site A, Inhibitor of cell wall synthesis site B, Inhibitor of cell wall synthesis site C, Inhibition of cellulose synthesis, Photosystem I electron diverter, Membrane disruptor (uncouplers), Inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD), Tyrosine Aminotransferase, Inhibition of dihydroorotate dehydrogenase(DHODH), HTS (homogentisate solanesyltransferase)-a downstream enzyme of HPPD, VLCAFE inhibitors, Inhibition of lycopene cyclase, Inhibition of Solanesyl Diphosphate Synthase (SDS), Inhibition of serine-threonine protein phosphatase or Herbicide with unknown mode of action or mixture thereof in an amount of 0.001 to 60% by weight;
c) an insecticide selected from the class of diamide, metadiamide or isoxazoline or mixture thereof in an amount 0.001 to 30% by weight; and
d) inactive formulation excipients.

2) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 1 wherein, herbicide from acetyl CoA Carboxylase (ACCase) Inhibitor is selected from Aryloxyphenoxy-propionate ('FOPs') including clodinafop-propargyl, cyhalofop-butyl, diclofop, fenoxaprop-P, fluazifop-P, haloxyfop, metamifop, propaquizafop, quizalofop-P-ethyl; Cyclohexanedione ('DIMs') including alloxydim, butroxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, tepraloxydim; and Phenylpyrazoline ('DEN') including pinoxaden or mixture thereof;
3) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 1 wherein, herbicide from:
a) acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor from Sulfonylurea group is selected from amidosulfuron, azimsulfuron, bensulfuron methyl, chlorimuron ethyl, chlorsulfuron, cinosulfuron, cloransulfuron methyl, cyclosulfamuron, ethametsulfuron methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron methyl sodium, foramsulfuron, halosulfuron methyl, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron mehtyl, nicosufulfuron, primisulfuron methyl, prosulfuron, pyrazosulfuron ehtyl, rimsulfuron, rimsulfuron, sulfometuron methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron methyl, trifloxysulfuron and triflusulfuron methyl;
b) acetoacetate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor from Pyrimidinyl(thio)benzoate group is selected from bispyribac-sodium, pyribenzoxim, pyrimisulfan, pyrithiobac sodium; from Triazolopyrimidine group selected from cloransulam-methyl, diclosulam, florasulam, flumetsulam, penoxsulam and pyroxsulam;
c) acetoacetate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor of Sulfonylaminocarbonyl group is selected from triazolinone-flucarbazone-sodium, propoxycarbazone-sodium, thiencarbazone-methyl; from Imidazolinone group such as imazamethabenz methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; from Sulfonanilides group is Triafamone;
d) synthetic Auxin of Phenoxy carboxylic acid group is selected from 2,4-D, 2,4-DB, dichloroprop, MCPA, MCPB, mecoprop; of Pyrimidine carboxylic acid group is selected from aminocyclopyrachlor; of Pyridine carboxylic acid group is selected from aminopyralid, clopyralid, fluroxypyr, picloram, triclopyr; of Benzoic acid group is dicamba; of Quinoline carboxylic acid group is quinclorac; and halauxifen methyl;
e) inhibitor of photosynthesis at photosystem II site A of Phenyl carbamate group is selected from desmedipham, phenmedipham; of Pyridazinone group is pyrazon; of Triazine group is selected from ametryn, atrazine, cyanazine, desmetryn, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazine, trietazine; of Triazinone group is selected from hexazione, metamitron, metribuzin; of Triazolinone group is amicarbazone; of Urea group is metoxuron; of Uracil group is group is selected from bromacil, terbacil;
f) inhibitor of photosynthesis at photosystem II site B of Benzothiadiazinone group is bentazone; of Nitrile group is selected from bromoxynil, ioxynil; of Phenyl-pyridazine group is pyridate;
g) inhibitor of lipid synthesis; not ACCase inhibition of Benzofuran group is ethofumesate; of Phosphorodithioate group is bensulie; of Thiocarbamate group is selected from butylate, cycloate, EPTC, esprocarb, molinate, pebulate, prosulfocarb, thiobencarb, triallate, vernolate;
h) inhibitor of 5-enolypyruvyl-shikimate-3-phosphate synthase (EPSPS) of Glycine group is Glyphosate;
i) inhibitor of glutamine synthetase of Phosphonic acid group is glufosinate;
j) inhibitor of phytoene desaturase (PDS) of Pyridinecarboxamide group is selected from diflufenican, picolinafen; of Pyridazinone group is norflurazon; and other compounds such as beflubutamid, fluridone, flurochloridone, flurtamone;
k) inhibitor of 1-deoxy-D-xyulose 5-phosphate sunthatase (DOXP synthase) of Isoxazolidinone group is clomazone;
l) inhibitor of protoporphyrinogen oxidase (Protox, PPO) of Dipheylether group is selected from aclifluorfen, bifenox, fluoroglycofen, fomesafen, lactofen, oxyfluorfen; of Triazolinone group is selected from azafenidin, carfentrazone-ethyl, flufenpyr-ethyl, sulfentrazone; of Pyrimidinedione group is selected from butafenacil, saflufenacil; of N-phenylphthalimide group is selected from flumiclorac, flumioxazin; of N-Phenyl-imide group is trifludimoxazin; of Thiadiazole group is fluthiacet-methyl; of Oxadiazole group is selected from oxadiargyl, oxadiazon; of Phenylpyrazole group is pyraflufen-ethyl, of other group is pyraclonil; of Uracil group is tiafenacil; of Pyrazole group is cyclopyranil;
m) mitosis Inhibitor of Chloroacetamide group is selected from acetochlor, alachlor, butachlor, dimethenamid, metazachlor, pretilachlor, propachlor, S-metolachlor, thenylchlor; of Tetrazolinone group is fentrazamide; of Oxyacetamide group is selected from flufenacet, mefenacet; of Acetamide group is napropamide; of Carbamate group is carbetamide and Other compound including anilofos;
n) inhibitor of 7, 8-dihydro-preroate synthetase (DHP) of Carbamate group is asulam;
o) inhibitor of indoleacetic acid transport of Phthalamate semicarbazone group is selected from diflufenzopyr and naptalam;
p) inhibitor of cell wall synthesis site A of Nitrile group is dichlobenil;
q) inhibitor of cell wall synthesis site B of Benzamide group is isoxaben;
r) inhibitor of cell wall synthesis site C of Alkylazines group is selected from indaziflam and triaziflam;
s) inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD) of Pyrazole group is selected from benzofenap, pyrasulfotole, pyrazolynate, pyrazoxyfen, tolpyralate; of Benzoylbicyclooctanedione group is benzobicyclon; Triketone group is selected from mesotrione, tembotrione, sulcotrione, tefuryltrione, fenquinotrione, lancotrione sodium; of Isoxazoles group is selected from isoxaflutole; bicyclo ring compound group is bicyclopyrone;
t) tyrosine Aminotransferase class is selected from cinmethylin and methiozolin;
u) inhibitors of dihydroorotate dehydrogenase (DHODH) is tetflupyrolimet;
v) HTS (homogentisate solanesyltransferase)-a downstream enzyme of HPPD is cyclopyrimorate;
w) VLCAFE inhibitors of Isoxazoline group is pyroxasulfone, of Triazolinone group is ipfencarbazone, of Trifluoromethansulfonanilides group is dimesulfazet, and other compound including fenoxasulfone;
x) inhibitors of lycopene cyclase is amitrole;
y) inhibitors of Solanesyl Diphosphate Synthase (SDS) is aclonifen;
z) inhibitors of serine-threonine protein phosphatase is endothall; and
aa) herbicide with unknown mode of action is selected from bromobutide, pelargonic acid, diphenamid, naproanilide, dalapon, copper (salt), epyrifenacil and bixzolone.
4) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 1 wherein, insecticide is selected from the class of diamide, metadiamides and isoxazoline as safener.

5) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 1 wherein, safener is selected from the cyprosulfamide, dietholate, isoxadifen / isoxadifen ethyl, dicyclonon, benoxacor, mefenpyr ethyl, fenchlorazole ethyl, cloquintocet / cloquintocet mexyl, oxabetrinil, naphthalic anhydride, mephenate, mefenpyr, furilazole, fluxofenim, flurazole, fenclorim, fenchlorazole, dichlormid or cyometrinil.

6) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 1, wherein the formulation for the said composition is selected from Capsule suspension (CS), Dispersible concentrate (DC), Emulsifiable concentrate (EC), Emulsion, water in oil (EO), Emulsion, oil in water (EW), Jambo balls or bags (bags in water soluble pouch), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (oil miscible suspension (OF), Oil miscible liquid (OL), Suspension concentrate (SC), Suspo-emulsion (SE), Soluble concentrate (SL), Water dispersible granule (WG or WDG), Water soluble granule (SG), Water soluble powder (SP), Wettable powder (WP), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZE), A mixed formulation of CS and EW (ZW), Granule (GR) / Soil Applied Granules (SAG), Controlled release granules (CR).

7) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 1 and claim 6, wherein the preferred composition for Oil Dispersion (OD) formulation comprises:
i. Oil Dispersion (OD) formulation of Cyhalofop-butyl 5%+ Penoxsulam ethyl 1%+ Chlorantraniliprole 1.5%;
ii. Oil Dispersion (OD) formulation of Cyhalofop-butyl 6%+ Tefuryltrione 4%+ Chlorantraniliprole 3%;
iii. Oil Dispersion (OD) formulation of Cyhalofop-butyl 6%+ Fenquinotrione 10%+ Chlorantraniliprole 3%;
iv. Oil Dispersion (OD) formulation of Cyhalofop-butyl 6%+ Lancotrion sodium 10%+ Chlorantraniliprole 3%;
v. Oil Dispersion (OD) formulation of Cyhalofop-butyl 6%+ Cyclopyrimorate 15%+ Chlorantraniliprole 3%;
vi. Oil Dispersion (OD) formulation of Cyhalofop-butyl 6%+ Tetflupyrolimet 15%+ Chlorantraniliprole 3%; and
vii. Oil Dispersion (OD) formulation of Cyhalofop-butyl 3%+ Bentazone 30%+ Chlorantraniliprole 3%.

8) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 7 wherein, Oil Dispersion (OD) formulation comprises:
a) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor or mixture thereof in an amount of 0.1 to 60% by weight;
b) one or more herbicide(s) selected from the group of Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor, Synthetic Auxin, Inhibitor of photosynthesis at photosystem II site A, Inhibitor of photosynthesis at photosystem II site B, Inhibitor of lipid synthesis; not ACCase inhibition, Inhibitor of 5-enolypyruvyl-shikimate-3-phosphate synthase (EPSPS), Inhibitor of glutamine synthetase: Phosphonic acid, Inhibitor of phytoene desaturase (PDS), Inhibitor of 1-deoxy-D-xyulose 5-phosphate sunthatase (DOXP synthase), Inhibitor of protoporphyrinogen oxidase (Protox, PPO), Mitosis Inhibitor, Inhibitor of 7,8-dihydro-preroate synthetase (DHP), Inhibitor of indoleacetic acid transport, Inhibitor of cell wall synthesis site A, Inhibitor of cell wall synthesis site B, Inhibitor of cell wall synthesis site C, Inhibition of cellulose synthesis, Photosystem I electron diverter, Membrane disruptor (uncouplers), Inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD), Tyrosine Aminotransferase, Inhibition of dihydroorotate dehydrogenase(DHODH), HTS (homogentisate solanesyltransferase)-a downstream enzyme of HPPD, VLCAFE inhibitors, Inhibition of lycopene cyclase, Inhibition of Solanesyl Diphosphate Synthase (SDS), Inhibition of serine-threonine protein phosphatase or Herbicide with unknown mode of action or mixture thereof in an amount of 0.001 to 60% by weight;
c) an insecticide selected from the class of diamide, metadiamide or isoxazoline or mixture thereof in an amount 0.001 to 30% by weight;
d) wetting agent in an amount of 35 to 40% by weight;
e) dispersing agent in an amount of 0.01 to 0.3% by weight;
f) buffering agent in an amount of 0.001 to 0.7% by weight;
g) antifoaming agent in an amount of 0.001 to 0.005% by weight;
h) preservative in an amount of 0.0001 to 0.0005% by weight;
i) anti-freezing agent in an amount of 0.04 to 0.08% by weight;
j) stabilizer in an amount of 0.001 to 3% by weight;
k) thickner in an amount of 0.001 to 0.5% by weight; and
l) carrier in an amount of 0.5 to 35% by weight.

9) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 8 wherein, wetting agent is selected from Ethoxylated alcohol, Alkylphenol alkoxylate, ethylene oxide/propylene oxide block copolymer, polyarylphenyl ether phosphate, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyldiphenyl sulfonates, Octyl phenol ethoxylate, alkyl phenol ethoxylate, sodium isopropyl naphthalene sulfonate, alkylnaphthalene sulfonate, organosilicons surfactants (as a wetting-spreading-penetrating agent) includes trisiloxane ethoxylate, Blend of alcohol ethoxylate and alkyl phenol ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, Ethoxylated tridecyl and/ or isotridecyl alcohol, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, may or may not be in modified form, may be liquid or powder form or mixture thereof.

10) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 8 wherein, dispersing agent is selected from Methylnaphthalene sulfonic acid -formaldehyde polymer sodium salt, Methyl oxirane, block copolymer, Methyl naphthalenes, Alkylaryl sulfonate, Acrylic copolymer blend, alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium ploycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, Acrylic graft copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, Polyarylphenyl ether sulphate ammonium salt oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide.

11) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 8 wherein, buffering agent is selected from EDTA-4NA, calcium hydroxyapatite, Acetic acid glacial, Potassium Dihydrogen Phosphate, Oleic acid, Citric acid, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase, Ammonium hydroxide and magnesium hydroxide.

12) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 8 wherein, antifoaming agent is selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethylsiloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane.

13) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 8 wherein, preservative is selected from 1,2-benzisothiazolin-3(2H)-one, 1,2-benzisothazol-3-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, formaldehyde, sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one, Lactic acid.

14) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 8 wherein, anti-freezing agent is selected from polyethylene glycols, methoxy polyethylene glycols, dipropylene glycol, polypropylene glycols, propylene glycol, polybutylene glycols, glycerine, ethylene glycol, Urea.

15) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 8 wherein, stabilizer is selected from Attapulgite clay, Bentonite clay.

16) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 8 wherein, thickner is selected from bentonite; magnesium aluminum silicate; and attapulgite; guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC); modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.

17) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 8 wherein, carrier is selected from water, water soluble alcohols and dihydroxy alcohol ethers, Solvent naphta (petrolium) heavy aromatic, Mixed xylene, Cyclohexanone, vegetable oil (plant, seed or tree) or its alkylated or ethoxylated or esterified. The alkylated vegetable oil may be methylated vegetable oil or ethylated vegetable oil. The vegetable oils include olive oil, kapok oil, castor oil, papaya oil, camellia oil, sesame oil, corn oil, rice bran oil, cotton seed oil, soybean oil, groundnut oil, rapeseed-mustard oil, linseed oil, tung oil, sunflower oil, safflower oil, coconut oil. The alkyl ester of vegetable oils includes methyl ester, ethyl ester, propyl ester or butyl ester of vegetable oils. Some of the examples are Methylated seed oil, polyalkyleneoxide modified polydimethylsiloxane alkylphenol ethoxylate, rapeseed oil methyl ester, rapeseed oil ethyl ester, rapeseed oil propyl esters, rapeseed oil butyl esters, soybean oil methyl ester, soybean oil ethyl ester, soybean oil propyl ester, soybean oil butyl ester, castor oil methyl ester, castor oil ethyl ester, castor oil propyl ester, castor oil butyl ester, cotton seed oil methyl ester, cotton seed oil ethyl ester, cotton seed oil butyl ester, cotton seed oil propyl ester, tall oil fatty acids esters-tallow methyl ester, tallow ethyl ester, tallow propyl ester, bio-diesel, mineral oil (aromatic solvents, isoparaffin, base solvent), fatty acid amides (e.g. C1 -C3 amines, alkylamines or alkanolamines with C6–C18 carboxylic acids), fatty acids, alkyl esters of fatty acids, methyl and ethyl oleate, methyl and ethyl soyate, alkyl benzenes and alkylnaphthalenes, polyalkylene glycol ethers, fatty acid diesters, fatty alkylamides and diamides, dialkylene carbonates, ketones and alcohols.

18) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 1 and claim 6, wherein the preferred composition for Suspo Emulsion (SE) formulation comprises:
i Suspo Emulsion (SE) formulation of Metamifop 6% + Tefuryltrione 4% + Tetraniliprole 4%;
ii Suspo Emulsion (SE) formulation of Metamifop 6% + Fenquinotrione 10% + Tetraniliprole 4%;
iii Suspo Emulsion (SE) formulation of Metamifop 6% + Lancotrion sodium 10% + Tetraniliprole 4%;
iv Suspo Emulsion (SE) formulation of Metamifop 6% + Cyclopyrimorate 15% + Tetraniliprole 4%;
v Suspo Emulsion (SE) formulation of Metamifop 6% + Tetflupyrolimet 15% + Tetraniliprole 4%;
vi Suspo Emulsion (SE) formulation of Metamifop 3% + Bentazone 30% + Tetraniliprole 2%; and
vii Suspo Emulsion (SE) formulation of Metamifop 7.5% + Bispyribac sodium 2% + Cyantraniliprole 6%.

19) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 18 wherein, Suspo Emulsion (SE) formulation comprises:
a) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor or mixture thereof in an amount of 0.1 to 60% by weight;
b) one or more herbicide(s) selected from the group of Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor, Synthetic Auxin, Inhibitor of photosynthesis at photosystem II site A, Inhibitor of photosynthesis at photosystem II site B, Inhibitor of lipid synthesis; not ACCase inhibition, Inhibitor of 5-enolypyruvyl-shikimate-3-phosphate synthase (EPSPS), Inhibitor of glutamine synthetase: Phosphonic acid, Inhibitor of phytoene desaturase (PDS), Inhibitor of 1-deoxy-D-xyulose 5-phosphate sunthatase (DOXP synthase), Inhibitor of protoporphyrinogen oxidase (Protox, PPO), Mitosis Inhibitor, Inhibitor of 7,8-dihydro-preroate synthetase (DHP), Inhibitor of indoleacetic acid transport, Inhibitor of cell wall synthesis site A, Inhibitor of cell wall synthesis site B, Inhibitor of cell wall synthesis site C, Inhibition of cellulose synthesis, Photosystem I electron diverter, Membrane disruptor (uncouplers), Inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD), Tyrosine Aminotransferase, Inhibition of dihydroorotate dehydrogenase(DHODH), HTS (homogentisate solanesyltransferase)-a downstream enzyme of HPPD, VLCAFE inhibitors, Inhibition of lycopene cyclase, Inhibition of Solanesyl Diphosphate Synthase (SDS), Inhibition of serine-threonine protein phosphatase or Herbicide with unknown mode of action or mixture thereof in an amount of 0.001 to 60% by weight;
c) an insecticide selected from the class of diamide, metadiamide or isoxazoline or mixture thereof in an amount 0.001 to 30% by weight;
d) wetting agent in an amount of 8 to 12% by weight;
e) wetting spreading and penetrating agent in an amount of 3 to 8% by weight;
f) dispersing agent in an amount of 1 to 7% by weight;
g) stabilizer in an amount of 0.001 to 4% by weight;
h) antifoaming agent in an amount of 0.1 to 0.5% by weight;
i) preservative in an amount of 0. 1 to 0.5% by weight;
j) anti-freezing agent in an amount of 3 to 8% by weight;
k) thickner in an amount of 0.12 to 0.18% by weight; and
l) carrier in an amount of 30 to 45% by weight.

20) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 19 wherein, wetting agent is selected from Ethoxylated alcohol, Alkylphenol alkoxylate, ethylene oxide/propylene oxide block copolymer, polyarylphenyl ether phosphate, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyldiphenyl sulfonates, Octyl phenol ethoxylate, alkyl phenol ethoxylate, sodium isopropyl naphthalene sulfonate, alkylnaphthalene sulfonate, organosilicons surfactants (as a wetting-spreading-penetrating agent) includes trisiloxane ethoxylate, Blend of alcohol ethoxylate and alkyl phenol ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, Ethoxylated tridecyl and/ or isotridecyl alcohol, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, may or may not be in modified form, may be liquid or powder form or mixture thereof.

21) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 19 wherein, dispersing agent is selected from Methylnaphthalene sulfonic acid -formaldehyde polymer sodium salt, Methyl oxirane, block copolymer, Methyl naphthalenes, Alkylaryl sulfonate, Acrylic copolymer blend, alkyl sulfonates, alkyl benzene sulfonates, alkyl aryl sulfonates, alkylphenolalkoxylates, tristyrylphenol ethoxylates, natural or synthetic fatty ethoxylate alcohols, natural or synthetic fatty acid alkoxylates, natural or synthetic fatty alcohols alkoxylates, alkoxylated alcohols (such as n-butyl alcohol poly glycol ether), block copolymers (such as ethylene oxide-propylene oxide block copolymers and ethylene oxide-butylene oxide block copolymers), fatty acid-polyalkylene glycol condensates, polyamine-fatty acid condensates, polyester condensates, salts of polyolefin condensates, sodium ligno sulfonate, sodium ploycarboxylate, EO/PO based copolymer, phenol sulfonate, sodium methyl oleoyl taurate, styrene acrylic acid copolymer, propyleneoxide-ethyleneoxide-copolymer, Acrylic graft copolymer, polyethylene glycol 2,4,6-tristyrylphenyl ether, tristyrylphenol-polyglycolether-phosphate, tristyrylphenole with 16 moles EO, tristyrylphenol-polyglycolether-phosphate, Polyarylphenyl ether sulphate ammonium salt oleyl-polyglycolether with ethylene oxide, tallow fattyamine polyethylene oxide, nonylphenol polyglycolether with 9-10 moles ethylene oxide.

22) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 19 wherein, stabilizer is selected from bentonite clay, butylated hydroxytoluene (BHT) and epoxidized soybean oil (ESBO), Epichlorhydrin.

23) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 19 wherein, antifoaming agent is selected from silicone oil, silicone compound, C10~C20 saturated fat acid compounds or C8~C10 aliphatic alcohols compound, silicone antifoam emulsion, dimethylsiloxane, polydimethyl siloxane, vegetable oil based antifoam, tallow based fatty acids, polyalkyleneoxide modified polydimethylsiloxane.

24) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 19 wherein, preservative is selected from 1,2-benzisothiazolin-3(2H)-one, 1,2-benzisothazol-3-one, sodium salt, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, formaldehyde, sodium o-phenylphenate, 5-chloro-2-methyl-4-isothiazolin-3-one & 2-methyl-4-isothiazolin-3-one, Lactic acid.

25) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 19 wherein, anti-freezing agent is selected from polyethylene glycols, methoxy polyethylene glycols, dipropylene glycol, polypropylene glycols, propylene glycol, polybutylene glycols, glycerine, ethylene glycol, Urea.

26) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 19 wherein, thickner is selected from bentonite; magnesium aluminum silicate; attapulgite, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC), modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.

27) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 19 wherein, carrier is selected from water, water soluble alcohols and dihydroxy alcohol ethers, Solvent naphta (petrolium) heavy aromatic, Mixed xylene, Cyclohexanone, vegetable oil (plant, seed or tree) or its alkylated or ethoxylated or esterified. The alkylated vegetable oil may be methylated vegetable oil or ethylated vegetable oil. The vegetable oils include olive oil, kapok oil, castor oil, papaya oil, camellia oil, sesame oil, corn oil, rice bran oil, cotton seed oil, soybean oil, groundnut oil, rapeseed-mustard oil, linseed oil, tung oil, sunflower oil, safflower oil, coconut oil. The alkyl ester of vegetable oils includes methyl ester, ethyl ester, propyl ester or butyl ester of vegetable oils. Some of the examples are Methylated seed oil, polyalkyleneoxide modified polydimethylsiloxane alkylphenol ethoxylate, rapeseed oil methyl ester, rapeseed oil ethyl ester, rapeseed oil propyl esters, rapeseed oil butyl esters, soybean oil methyl ester, soybean oil ethyl ester, soybean oil propyl ester, soybean oil butyl ester, castor oil methyl ester, castor oil ethyl ester, castor oil propyl ester, castor oil butyl ester, cotton seed oil methyl ester, cotton seed oil ethyl ester, cotton seed oil butyl ester, cotton seed oil propyl ester, tall oil fatty acids esters-tallow methyl ester, tallow ethyl ester, tallow propyl ester, bio-diesel, mineral oil (aromatic solvents, isoparaffin, base solvent), fatty acid amides (e.g. C1 -C3 amines, alkylamines or alkanolamines with C6–C18 carboxylic acids), fatty acids, alkyl esters of fatty acids, methyl and ethyl oleate, methyl and ethyl soyate, alkyl benzenes and alkylnaphthalenes, polyalkylene glycol ethers, fatty acid diesters, fatty alkylamides and diamides, dialkylene carbonates, ketones and alcohols.

28) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 1 and claim 6, wherein the preferred composition for EC (Emulsifiable concentrate) formulation comprises:
i EC (Emulsifiable concentrate) formulation of Clodinafop Propargyl 8% + Acifluorfen 16.5% + Chlorantraniliprole 3%;
ii EC (Emulsifiable concentrate) formulation of Propaquizafop 5% + Oxyfluorfen 12% + Chlorantraniliprole 3.4%;
iii EC (Emulsifiable concentrate) formulation of Clodinafop Propargyl 8% + Acifluorfen 16.5% + Broflanilide 1.2%;
iv EC (Emulsifiable concentrate) formulation of Propaquizafop 5% + Oxyfluorfen 12% + Broflanilide 1.33%;
v EC (Emulsifiable concentrate) formulation of Haloxyfop R methyl 8% + Imazethapyr 7% + Chlorantraniliprole 3%;
vi EC (Emulsifiable concentrate) formulation of Haloxyfop R methyl 8% + Imazamox 7% + Chlorantraniliprole 3%;
vii EC (Emulsifiable concentrate) formulation of Haloxyfop R methyl 8% + Acifluorfen sodium 16.5% + Chlorantraniliprole 3%;
viii EC (Emulsifiable concentrate) formulation of Haloxyfop R methyl 8% + Fomesafen sodium 18% + Chlorantraniliprole 3%;
ix EC (Emulsifiable concentrate) formulation of Haloxyfop R methyl 8% + Lactofen 18% + Chlorantraniliprole 3%;
x EC (Emulsifiable concentrate) formulation of Haloxyfop R methyl 8% + Fluthiacet methyl 1.35% + Chlorantraniliprole 3%; and
xi EC (Emulsifiable concentrate) formulation of Quizalofop ethyl 4% + Pyrithiobac sodium 6% + Chlorantraniliprole 3%.
29) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 28 wherein, EC (Emulsifiable concentrate) formulation comprises:
a) a herbicide selected from Acetyl CoA Carboxylase (ACCase) Inhibitor or mixture thereof in an amount of 0.1 to 60% by weight;
b) one or more herbicide(s) selected from the group of Acetolactate Synthase (ALS) or Acetohydroxy Acid Synthase (AHAS) inhibitor, Synthetic Auxin, Inhibitor of photosynthesis at photosystem II site A, Inhibitor of photosynthesis at photosystem II site B, Inhibitor of lipid synthesis; not ACCase inhibition, Inhibitor of 5-enolypyruvyl-shikimate-3-phosphate synthase (EPSPS), Inhibitor of glutamine synthetase: Phosphonic acid, Inhibitor of phytoene desaturase (PDS), Inhibitor of 1-deoxy-D-xyulose 5-phosphate sunthatase (DOXP synthase), Inhibitor of protoporphyrinogen oxidase (Protox, PPO), Mitosis Inhibitor, Inhibitor of 7,8-dihydro-preroate synthetase (DHP), Inhibitor of indoleacetic acid transport, Inhibitor of cell wall synthesis site A, Inhibitor of cell wall synthesis site B, Inhibitor of cell wall synthesis site C, Inhibition of cellulose synthesis, Photosystem I electron diverter, Membrane disruptor (uncouplers), Inhibitor of Hydroxyphenyl Pyruvate Dioxygenase (4-HPPD), Tyrosine Aminotransferase, Inhibition of dihydroorotate dehydrogenase(DHODH), HTS (homogentisate solanesyltransferase)-a downstream enzyme of HPPD, VLCAFE inhibitors, Inhibition of lycopene cyclase, Inhibition of Solanesyl Diphosphate Synthase (SDS), Inhibition of serine-threonine protein phosphatase or Herbicide with unknown mode of action or mixture thereof in an amount of 0.001 to 60% by weight;
c) an insecticide selected from the class of diamide, metadiamide or isoxazoline or mixture thereof in an amount 0.001 to 30% by weight;
d) wetting agent in an amount of 0.5 to 0.8% by weight;
e) emulsifier in an amount of 3 to 8% by weight; and
f) solvent in an amount of 10 to 50% by weight.

30) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 29 wherein, wetting agent is selected from Ethoxylated alcohol, Alkylphenol alkoxylate, ethylene oxide/propylene oxide block copolymer, polyarylphenyl ether phosphate, ethoxylated fatty alcohol, sodium dioctyl sulfosuccinate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate, alkyldiphenyl sulfonates, Octyl phenol ethoxylate, alkyl phenol ethoxylate, sodium isopropyl naphthalene sulfonate, alkylnaphthalene sulfonate, organosilicons surfactants (as a wetting-spreading-penetrating agent) includes trisiloxane ethoxylate, Blend of alcohol ethoxylate and alkyl phenol ethoxylate, polydimethylsiloxane, polyoxyethylene methyl polysiloxane, Ethoxylated tridecyl and/ or isotridecyl alcohol, polyoxyalkylene methyl polysiloxane, polyether polymethyl siloxane copolymer, heptamethyl trisiloxane, Polyalkyleneoxide modified heptamethyl trisiloxane, polyether modified polysiloxane, may or may not be in modified form, may be liquid or powder form or mixture thereof.

31) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 29 wherein, emulsifier is selected from salts of dodecylbenzene sulphonate, e.g. Ca-salts or amine salts, and sulphonates of other C11-C16 alkylbenzenes, alkylether sulphates, alkylphenoletherphosphates and ester phosphates; non-ionic surfactants such as alkoxylated alcohols and alkylphenols, ethoxylated fatty acids, ethoxylated vegetable oils, e.g. ethoxylated castor oil, fatty acid esters, e.g. of sorbitol, and their ethoxylated derivatives, ethoxylated amines, and condensates of glycerol; and catanionic emulsifiers such as a cationic amine, optionally in combination with an alkylsulphonate or ether sulphonate or ether phosphate, alkoxylated alcohols; alkoxylated alkylphenols; ethoxylated fatty acids; ethoxylated vegetable oils; ethoxylated tristyrylphenol; fatty acid esters of sorbitol and ethoxylated derivatives thereof; ethoxylated amines and condensates of glycerol; sulfonated alkylbenzenes in the range C11-C16 and salts thereof; alkylether sulphates; alkyletherphosphates; alkylphenoletherphosphates; or combinations thereof; salts of phosphate esters of ethoxylated tristyrylphenol; salts of sulphated ethers of ethoxylated tristyrylphenol; or a catanionic system, wherein a cationic amine is present in combination with an alkylsulphonate, an alkylethersulphonate, an ether sulphate, or an ether phosphate such as an alkyletherphosphate, Polysorbate 20, nonylphenol polyethoxy ethanols, castor oil polyglycol ethers, polyadducts of ethylene oxide and polypropylene, tributyl phenoxy polyethoxy ethanol, octyl phenoxy polyethoxy ethanol.

32) The synergistic agrochemical composition with insecticide for reducing phytotoxicity in crops as claimed in claim 29 wherein, solvent is selected from Mixture of heavy aromatic hydrocarbons / C IX, xylene, n-butanol, solvent C-9, N-methyl 2-pyrrolidine, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, Paraffinic hydrocarbons, cyclohexanone, isophorone and ester solvents such as methyloleate, dimethylamide and morpholineamide derivatives of C6-C16 fatty acids, and mono-alkylene carbonates such as ethylene carbonate, propylene carbonate and butylene carbonates, dimethylsulfoxide (DMSO), 2-ethylhexanol and n-butanol, n-alkylpyrrolidones, fatty acid dimethyl esters, fatty acid esters, dibasic esters, aromatic hydrocarbons and/or aliphatic hydrocarbons, one or more dimethylamides, such as C8-dimethylamide, C10-dimethylamide, C12-dimethylamide, ethylene glycol, propylene glycol, polyalkylene glycols, aromatic hydrocarbons, methylpyrrolidinone (NMP); dimethylformamide (DMF); dimethylisosorbide (DMI); isophorone; acetophenone; 1,3-dimethyl-2-imidazolidonone; lactate esters; dimethyl and diethylcarbonates; alcohols including methanol; ethanol; iso-propanol; n-propanol; n-butanol; iso-butanol; and tert-butanol; Methyl L-lactate, 2-Ethylhexyl L-lactate, Ethyl L-lactate, n-Butyl L-lactate, Octyl phenyl ethoxylates.

Documents

Orders

Section Controller Decision Date

Application Documents

# Name Date
1 202011037841-IntimationOfGrant07-02-2024.pdf 2024-02-07
1 202011037841-STATEMENT OF UNDERTAKING (FORM 3) [02-09-2020(online)].pdf 2020-09-02
2 202011037841-PatentCertificate07-02-2024.pdf 2024-02-07
2 202011037841-PROVISIONAL SPECIFICATION [02-09-2020(online)].pdf 2020-09-02
3 202011037841-POWER OF AUTHORITY [02-09-2020(online)].pdf 2020-09-02
3 202011037841-AMMENDED DOCUMENTS [06-02-2024(online)].pdf 2024-02-06
4 202011037841-FORM FOR SMALL ENTITY(FORM-28) [02-09-2020(online)].pdf 2020-09-02
4 202011037841-FORM 13 [06-02-2024(online)].pdf 2024-02-06
5 202011037841-MARKED COPIES OF AMENDEMENTS [06-02-2024(online)].pdf 2024-02-06
5 202011037841-FORM FOR SMALL ENTITY [02-09-2020(online)].pdf 2020-09-02
6 202011037841-Written submissions and relevant documents [06-02-2024(online)].pdf 2024-02-06
6 202011037841-FORM 1 [02-09-2020(online)].pdf 2020-09-02
7 202011037841-EVIDENCE FOR REGISTRATION UNDER SSI(FORM-28) [02-09-2020(online)].pdf 2020-09-02
7 202011037841-Correspondence to notify the Controller [22-01-2024(online)].pdf 2024-01-22
8 202011037841-US(14)-HearingNotice-(HearingDate-23-01-2024).pdf 2023-12-22
8 202011037841-EVIDENCE FOR REGISTRATION UNDER SSI [02-09-2020(online)].pdf 2020-09-02
9 202011037841-AMMENDED DOCUMENTS [04-09-2023(online)].pdf 2023-09-04
9 202011037841-DECLARATION OF INVENTORSHIP (FORM 5) [02-09-2020(online)].pdf 2020-09-02
10 202011037841-FORM 13 [04-09-2023(online)].pdf 2023-09-04
10 202011037841-RELEVANT DOCUMENTS [31-07-2021(online)].pdf 2021-07-31
11 202011037841-FORM 13 [31-07-2021(online)].pdf 2021-07-31
11 202011037841-MARKED COPIES OF AMENDEMENTS [04-09-2023(online)].pdf 2023-09-04
12 202011037841-ENDORSEMENT BY INVENTORS [31-07-2021(online)].pdf 2021-07-31
12 202011037841-Response to office action [04-09-2023(online)].pdf 2023-09-04
13 202011037841-CORRESPONDENCE-OTHERS [31-07-2021(online)].pdf 2021-07-31
13 202011037841-SER.pdf 2023-08-08
14 202011037841-ABSTRACT [15-05-2023(online)].pdf 2023-05-15
14 202011037841-COMPLETE SPECIFICATION [31-07-2021(online)].pdf 2021-07-31
15 202011037841-CLAIMS [15-05-2023(online)].pdf 2023-05-15
15 202011037841-OTHERS-070920.pdf 2021-10-19
16 202011037841-COMPLETE SPECIFICATION [15-05-2023(online)].pdf 2023-05-15
16 202011037841-OTHERS-070920-.pdf 2021-10-19
17 202011037841-FER_SER_REPLY [15-05-2023(online)].pdf 2023-05-15
17 202011037841-Correspondence-070920.pdf 2021-10-19
18 202011037841-OTHERS [15-05-2023(online)].pdf 2023-05-15
18 202011037841-RELEVANT DOCUMENTS [23-03-2022(online)].pdf 2022-03-23
19 202011037841-FER.pdf 2022-11-15
19 202011037841-POA [23-03-2022(online)].pdf 2022-03-23
20 202011037841-FORM 13 [23-03-2022(online)].pdf 2022-03-23
20 202011037841-FORM 18A [19-07-2022(online)].pdf 2022-07-19
21 202011037841-AMMENDED DOCUMENTS [23-03-2022(online)].pdf 2022-03-23
21 202011037841-FORM28 [19-07-2022(online)].pdf 2022-07-19
22 202011037841-MSME CERTIFICATE [19-07-2022(online)].pdf 2022-07-19
22 202011037841-PA [24-03-2022(online)].pdf 2022-03-24
23 202011037841-8(i)-Substitution-Change Of Applicant - Form 6 [24-03-2022(online)].pdf 2022-03-24
23 202011037841-FORM28 [24-03-2022(online)].pdf 2022-03-24
24 202011037841-ASSIGNMENT DOCUMENTS [24-03-2022(online)].pdf 2022-03-24
25 202011037841-FORM28 [24-03-2022(online)].pdf 2022-03-24
25 202011037841-8(i)-Substitution-Change Of Applicant - Form 6 [24-03-2022(online)].pdf 2022-03-24
26 202011037841-MSME CERTIFICATE [19-07-2022(online)].pdf 2022-07-19
26 202011037841-PA [24-03-2022(online)].pdf 2022-03-24
27 202011037841-AMMENDED DOCUMENTS [23-03-2022(online)].pdf 2022-03-23
27 202011037841-FORM28 [19-07-2022(online)].pdf 2022-07-19
28 202011037841-FORM 13 [23-03-2022(online)].pdf 2022-03-23
28 202011037841-FORM 18A [19-07-2022(online)].pdf 2022-07-19
29 202011037841-FER.pdf 2022-11-15
29 202011037841-POA [23-03-2022(online)].pdf 2022-03-23
30 202011037841-OTHERS [15-05-2023(online)].pdf 2023-05-15
30 202011037841-RELEVANT DOCUMENTS [23-03-2022(online)].pdf 2022-03-23
31 202011037841-Correspondence-070920.pdf 2021-10-19
31 202011037841-FER_SER_REPLY [15-05-2023(online)].pdf 2023-05-15
32 202011037841-COMPLETE SPECIFICATION [15-05-2023(online)].pdf 2023-05-15
32 202011037841-OTHERS-070920-.pdf 2021-10-19
33 202011037841-CLAIMS [15-05-2023(online)].pdf 2023-05-15
33 202011037841-OTHERS-070920.pdf 2021-10-19
34 202011037841-ABSTRACT [15-05-2023(online)].pdf 2023-05-15
34 202011037841-COMPLETE SPECIFICATION [31-07-2021(online)].pdf 2021-07-31
35 202011037841-CORRESPONDENCE-OTHERS [31-07-2021(online)].pdf 2021-07-31
35 202011037841-SER.pdf 2023-08-08
36 202011037841-Response to office action [04-09-2023(online)].pdf 2023-09-04
36 202011037841-ENDORSEMENT BY INVENTORS [31-07-2021(online)].pdf 2021-07-31
37 202011037841-FORM 13 [31-07-2021(online)].pdf 2021-07-31
37 202011037841-MARKED COPIES OF AMENDEMENTS [04-09-2023(online)].pdf 2023-09-04
38 202011037841-FORM 13 [04-09-2023(online)].pdf 2023-09-04
38 202011037841-RELEVANT DOCUMENTS [31-07-2021(online)].pdf 2021-07-31
39 202011037841-AMMENDED DOCUMENTS [04-09-2023(online)].pdf 2023-09-04
39 202011037841-DECLARATION OF INVENTORSHIP (FORM 5) [02-09-2020(online)].pdf 2020-09-02
40 202011037841-EVIDENCE FOR REGISTRATION UNDER SSI [02-09-2020(online)].pdf 2020-09-02
40 202011037841-US(14)-HearingNotice-(HearingDate-23-01-2024).pdf 2023-12-22
41 202011037841-Correspondence to notify the Controller [22-01-2024(online)].pdf 2024-01-22
41 202011037841-EVIDENCE FOR REGISTRATION UNDER SSI(FORM-28) [02-09-2020(online)].pdf 2020-09-02
42 202011037841-Written submissions and relevant documents [06-02-2024(online)].pdf 2024-02-06
42 202011037841-FORM 1 [02-09-2020(online)].pdf 2020-09-02
43 202011037841-MARKED COPIES OF AMENDEMENTS [06-02-2024(online)].pdf 2024-02-06
43 202011037841-FORM FOR SMALL ENTITY [02-09-2020(online)].pdf 2020-09-02
44 202011037841-FORM FOR SMALL ENTITY(FORM-28) [02-09-2020(online)].pdf 2020-09-02
44 202011037841-FORM 13 [06-02-2024(online)].pdf 2024-02-06
45 202011037841-POWER OF AUTHORITY [02-09-2020(online)].pdf 2020-09-02
45 202011037841-AMMENDED DOCUMENTS [06-02-2024(online)].pdf 2024-02-06
46 202011037841-PROVISIONAL SPECIFICATION [02-09-2020(online)].pdf 2020-09-02
46 202011037841-PatentCertificate07-02-2024.pdf 2024-02-07
47 202011037841-IntimationOfGrant07-02-2024.pdf 2024-02-07
47 202011037841-STATEMENT OF UNDERTAKING (FORM 3) [02-09-2020(online)].pdf 2020-09-02

Search Strategy

1 SearchHistoryE_11-08-2022.pdf

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