DESC:FIELD OF THE INVENTION:
The present invention relates to synergistic herbicidal composition comprising A) Cycloxydim B) at least one herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-5 Butyl, Propaquizafop and Haloxyfop-R-Methyl C) at least one more herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox,Chlorimuron Ethyl and Fluthiacet methyl with one or more inactive excipients. The present invention also relates to process for preparing the said composition and its use as herbicide. 10 BACKGROUND OF THE INVENTION
Cycloxydim is a systemic herbicide approved for use in the EU. It is moderately 15 soluble in aqueous solution, is unlikely to leach to ground water and is relatively volatile. It is not persistent in soils and is unlikely to persist in aquatic systems due to rapid aqueous photolysis. It has a low mammalian toxicity and, whilst the chemical properties suggest it may bio accumulate, that does not appear to happen in practice. Chemically known as 20 (5RS)-2-[(EZ)-1-(ethoxyimino)butyl]-3-hydroxy-5-[(3RS)-thian-3-yl]cyclohex-2-en-1-one and chemical structure is as below;
25
Clodinafop Propargyl which is chemically known as propyny(R)-2-[4-[(5-chloro-3-fluoro-2-pyridinyl)oxy] phenoxy] propionate is a selective systemic post emergence herbicide, used for the control of grassy weeds in cereals mainly
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wheat. It belongs to aryloxyphenoxy propionate class of herbicide, acts by inhibition of acetyl COA carboxylase.
Quizalofop-p-ethyl (QPE) is a post-emergence herbicide that effectively controls grass weeds and is often detected in the environment. Quizalofop-p-ethyl (QPE; 5 ethyl(R)-2-[4-(6-chloroquinoxalin-2-yloxy) phenoxy] propionate) is a member of the aryloxyphenoxypropionate (AOPP) group of herbicides. Like other members of this family, QPE is a selective post-emergence herbicide that is registered for use in the control of annual and perennial grass weeds in crops of potatoes, soya beans, sugar beets, peanuts, oilseed rape, sunflowers, vegetables, cotton, flax, and 10 other broad leafed plants. As a systemic herbicide that inhibits acetyl CoA carboxylase, QPE is absorbed from the leaf surface and translocated throughout the plant via the xylem and phloem, from the treated foliage to the root system, and accumulates in the meristematic tissue, thus inhibiting fatty acid biosynthesis
15
Quizalofop-P-tefuryl is a new APP post-emergence herbicide used for the control of the grass weeds in industrial and horticultural crops. The 40 g/l EC formulation shows a favourable toxicological and environmental profile. The active ingredient shows a very good systemic activity; it is rapidly adsorbed by the leaves of grass weeds, producing their yellowishing and consequent death. It 20 is used at 40-80 g/ha of active ingredient. At these dosages shows a very good herbicide activity against many annual and perennial grass weeds,
Fenoxaprop-p-ethyl as active ingredient which is a selective herbicide having action against Echinochloa sp. and other grassy weeds in soybean, rice, cotton, 25 black gram and onion. It is a post-emergent herbicide having action on broad spectrum of grasses. Fenoxaprop-p-ethyl is quickly taken up by the leaves and stems of the grassy weeds.
30
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Fluazifop-p-butyl is a selective phenoxy herbicide and chemically known as (R)2-[4[445[-(trifluoro-methyl)-2-pyridinyl]oxy]-phenoxy] propanoate. It is used for post-emergence control of annual and perennial grass weeds. It is used on soybeans and other broad-leaved crops such as carrots, spinach, potatoes, and ornamentals 5
Propaquizafop is a synthetic compound of the chemical family the aryloxyphenoxypropionate. Propaquizafop acts as a systemic herbicide of annual and perennial grasses. It is applied as a foliar spray and, being quickly absorbed through the leaves and translocated to the meristematic growing regions of the 10 plants, where it inhibits cell growth and division through the inhibition of ACCase inhibition. Propaquizafop can be used on a wide range of broad-leaved crops, including sugar beet, oilseed rape, soybeans, sunflower, other field crops, vegetables, fruit trees, vineyards and forestry.
15
Haloxyfop-R-Methyl is a selective Herbicide, absorbed by the foliage and roots, and hydrolysed to Haloxyfop-R, which is translocated to meristematic tissues and inhibits their growth.Haloxyfop-R-methyl is used post-emergence for control of annual and perennial grasses in sugar beet, fodder beet, oilseed rape, potatoes, leaf vegetables, onions, flax, sunflowers, soya beans, vines, strawberries, and 20 other crops.
Acifluorfen is an herbicide. It is effective against broadleaf weeds and grasses and is used agriculturally on fields growing soybeans, peanuts, peas, and rice. 25 Acifluorfen-sodium is an herbicide that is currently not approved for EU use. It is highly soluble in water and in many organic solvents. It is volatile. It may leach to groundwater under certain conditions. It is moderately persistence in soil systems and can be very persistent in aquatic systems. It has a moderate mammalian toxicity and there is some concern regarding its potential for 30 bioaccumulation. It is a recognised irritant. Acifluorfen-sodium is moderately
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toxic to birds, honeybees and most aquatic organisms. It is relatively non-toxic to earthworms.
Fomesafen herbicide is a selective herbicide which may be applied pre-plant, pre-emergence or post-emergence for control or partial control of broadleaf weeds, 5 grasses and sedges in soybeans.
Lactofen is a complex ester of acifluorfen and is a nitrophenyl ether selective herbicide. It is used in post-emergence applications to certain crops which are resistant to its action. Lactofen is applied as a foliar spray and is commonly used 10 to control broadleaved weeds in soybean, cereals, potatoes and peanuts. It may be combined with oil or fertilizer adjuvants and surfactants. Some formulations include solvents such as xylenes and cumene. Lactofen is available in solid form or as an emulsifiable concentrate. Lactofen has a very low solubility in water and is not expected to contaminate surface waters. It binds tightly to soil and is then 15 broken down in between one and seven days
Bentazon, 3-(1-methylethyl)-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide, is a herbicide used in agriculture for control of broadleaf weeds in crops such as soybeans, rice, corn, peanuts, and lima beans. As summarized from U.S. EPA reports (1998b,g), bentazon is not chemically reactive and no highly reactive 20 species have been identified during its metabolism. Bentazon was negative in bacterial mutation assays, in a mammalian cell assay, in the unscheduled DNA synthesis assay, and in the mouse micronucleus assay in vivo. Bentazon is a colorless to white crystalline powder. Commercial product can be a soluble concentrate that may be mixed with water and used as a spray. 25
Imazethapyr belongs to the chemical group Imidazolinone and acts by inhibiting the Acetolactate Synthase (ALS), an enzyme which is Important in protein synthesis within the plant. This leads to disruption of the DNA synthesis and cell growth. Imazethapyr is chemically known as 5-ethyl-2-[(RS)-4-isopropyl-4-30 methyl-5-oxo-2-imidazolin-2-yl]nicotinic acid and is an active compound from
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the group of imidazolinone herbicides, which are known e.g. from Shaner, D. L, O' Conner, S.L, The Imidazolinone Herbicides, CRC Press Inc., Boca Raton, Florida 1991 and also from The Compendium of Pesticide Common. it is taken up by the weeds through roots and the leaves. Solitude has sufficient residual effect to give weed control not only in the early stages but also in subsequent 5 flushes.
Imazamox is a member of the imidazolinone class of herbicides. It is registered for post-emergence control of broadleaf weeds and grass in alfalfa, edible legumes and soybeans. It is a systemic herbicide that moves throughout the plant 10 tissue and prevents plants from producing an essential enzyme, acetolactate synthase (ALS), which is not found in animals. This enzyme is key for the biosynthesis of branched chain amino acids. Susceptible plants will stop growing soon after treatment, but plant death and decomposition will occur over several weeks. 15
Chlorimuron Ethylherbicide, is a selective, post-emergent herbicide for weed control in soybean (both broad leaf weeds and sedges) cultivation in India. It offers ingredients that provide farmers effective crop protection with an easy application. It delivers flexible solutions for stubborn weeds such as P.niruri, 20 C.rotundus, C.benghalensis, etc in soybean cultivation. It exhibits both residual and contact soil activity. Once taken up by a susceptible species, the herbicide is rapidly translocated throughout the plant, inhibiting the shoot and root growth of weeds. Susceptible weed plants will cease to grow immediately after post emergence treatment and are killed within 7-14 days. 25
Because of the multitude of possible influencing factors, there is virtually no individual active substance which combines in itself the properties desired for different requirements, in particular with regard to the harmful plant species and 30 the climatic zones. In addition, there is the constant problem of achieving the
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effect with an ever lower herbicide application rate. A lower application rate reduces not only the amount of an active substance required for the application but generally also reduces the amounts of formulation auxiliaries necessary. Both reduce the economic cost and improve the ecological compatibility of the herbicide treatment. 5
EP3187049 relates to a herbicidal composition comprising: A) at least one herbicidal compound A from the class of ACC inhibitors which is cycloxydim and B) at least one herbicidal compound B selected from groups b0) 10 to b8) defined according to the description. The invention also relates to agrochemical compositions comprising the herbicidal compositions according to the invention, to processes for preparation of the herbicidal and agrochemical compositions, to their use for controlling unwanted vegetation and to the methods of use. 15
EP3091834A1The present invention relates to herbicidally active compositions, which comprise 5-ethyl-2- [(RS)-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl]nicotinic acid (common name: imazethapyr) and (5RS)-2-[(EZ)-1-(Ethoxyimino)butyl]-3-hydroxy-5- [(3RS)-thian-3-yl]cyclohex-2-en-1-one 20 (common name: cycloxydim) and optionally 2-[(RS)-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl]-5-methoxymethylnicotinic acid (common name: imazamox).
CN103548830A relates to the field of pesticide preparations and particularly 25 relates to an herbicidal composition and a preparation thereof. The herbicidal composition comprises flumiclorac-penty and cycloxydim. The herbicidal composition and the preparation thereof, provided by the invention, can realize a significant synergistic effect, expand a herbicide controlling spectrum and greatly reduce the dosage and number of administration times, have the advantages of 30 broad using period, safety, high efficiency, long lasting period, environmental friendliness and the like, and can further delay the production of drug resistance
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of weeds, effectively control most of the weeds in corn fields and strengthen the control effect against broadleaf weeds and gramineous weeds.
CN106359384A relates to ternary herbicidally active compositions, which comprise a) 5- ethyl-2-[(RS)-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-5 yl]nicotinic acid (common name: imazethapyr) and 2-[(RS)-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl]-5- methoxymethylnicotinic acid (common name: imazamox) and b) at least one herbicide selected from the group consisting of 5-(2-chloro-a,a,a-trifluoro-p- tolyloxy)-N-mesyl-2-nitrobenzamide (common name: fomesafen), 2',4'-dichloro-5'-(4-difluoromethyl-4,5-dihydro-3-methyl-5-10 oxo-1 H-1,2,4-triazoM - yl)methanesulfonanilide (common name: sulfentrazone) and 3-isopropyl-1 H-2,1,3- benzothiadiazin-4(3H)-one 2,2-dioxide (common name: bentazone).
Indian application 201617026747 describes relates to herbicidally active 15 compositions which comprise 5 ethyl 2 [(RS) 4 isopropyl 4 methyl 5 oxo 2 imidazolin 2 yl]nicotinic acid (common name: imazethapyr) and (5RS) 2 [(EZ) 1 (Ethoxyimino)butyl] 3 hydroxy 5 [(3RS) thian 3 yl]cyclohex 2 en 1 one (common name: cycloxydim) and optionally 2 [(RS) 4 isopropyl 4 methyl 5 oxo 2 imidazolin 2 yl] 5 methoxymethylnicotinic acid (common name: imazamox). 20
However still there is a need for a synergistic herbicidal composition which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process and exhibits synergism.
25 Inventors of the present invention have surprisingly found that the synergistic herbicidal composition comprising A) Cycloxydim B) at least one herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl C) at least one more herbicide selected from Acifluorfen, Fomesafen, Lactofen, 30 Bentazon, Imazethapyr, Imazamox, Chlorimuron Ethyl and Fluthiacet
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methylwith one or more inactive excipients described herein in can provide solution to the above mentioned problems. SUMMARY OF THE INVENTION 5 It is an aspect of the present invention is to provide, with a view to effective resistance management and effective control of weeds especially grassy weeds, at application rates which are as low as possible, compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful weeds and a broadened activity spectrum, in particular for certain 10 indications.
We have accordingly found that this object is achieved by synergistic herbicidal composition comprising A) Cycloxydim B) at least one herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-15 P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl C) at least one more herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox, Chlorimuron Ethyl and Fluthiacet methyl with one or more inactive excipients.
20 Accordingly, in a main aspect of the present invention provides a synergistic herbicidal composition comprising A) Cycloxydim B) at least one herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl C) at least one more herbicide selected from Acifluorfen, Fomesafen, Lactofen, 25 Bentazon, Imazethapyr, Imazamox, Chlorimuron Ethyl and Fluthiacet methylwith one or more inactive excipients.
Accordingly, in a second aspect, the present invention provides a method of preparing the synergistic herbicidal composition comprising A) Cycloxydim B) 30 at least one herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop
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and Haloxyfop-R-Methyl C) at least one more herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox, Chlorimuron Ethyl and Fluthiacet methylwith one or more inactive excipients.
DETAILED DESCRIPTION OF THE INVENTION 5
The present invention provides solution to all the problems mentioned above by providing the synergistic herbicidal composition.
The present invention provides a synergistic herbicidal composition comprising 10 A) Cycloxydim B) at least one herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl C) at least one more herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox, Chlorimuron Ethyl and Fluthiacet methylwith one or more inactive 15 excipients.
"Effective amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficient to effect such treatment.
20 The term “formulation” and “composition” as used herein conveys the same meaning and can be used interchangeably.
As used herein, the term "synergistic" means a combination of components wherein the activity of the combination is greater than the sum of the individual 25 activities of each component of the combination. As per one embodiment, the active herbicidal compound as mentioned above to be used in the composition of present invention can be in the form of base or any salts form known in the art. 30
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The formulation or composition of the present invention can be in various physical forms, for example in the form of a dustable powder (DP), a gel, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), an emulsifiable concentrate (EC), a micro- emulsifiable concentrate, an 5 oil-in-water emulsion (EW), an oil flowable ( a spreading oil (SO)), an aqueous dispersion ( aqueous suspension concentrate (SC)), an oily dispersion (OD), a suspo-emulsion (SE),Micro Emulsion (ME), a capsule suspension (CS), a soluble liquid, a water-soluble concentrate (with water or a water-miscible organic solvent as carrier), ZC (Mixed formulation of CS and SC), ZE (Mixed 10 formulation of CS and SE), ZW (Mixed formulation of CS and EW).
In a preferred embodiment, the composition of present invention is selected from Suspension Concentrate (SC), Suspo emulsion (SE), Micro Emulsion (ME),Capsule Suspension (CS), Oil Dispersion (OD), mixed formulation of CS 15 and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), Water Soluble Granules (SG), Water dispersible granule (WDG or WG), Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP).
20 As per one embodiment, the synergistic herbicidal composition comprising A) Cycloxydim B) at least one herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl C) at least one more herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, 25 Imazamox, Chlorimuron Ethyl and Fluthiacet methylwith one or more inactive excipients, wherein active ingredients are present in concentration as described below;
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Compound A
Compound B
Compound C
Active Ingredient
Cycloxydim
Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl,
Propaquizafop, Haloxyfop-R-Methyl
Acifluorfen, Fomesafen,
Lactofen,
Bentazon, Imazethapyr, Imazamox, Chlorimuron Ethyl
Fluthiacet methyl Concentration
0.1-25%
0.1-25%
0.1-50%
In another embodiment of the present invention the synergistic herbicidal composition comprising A) Cycloxydim B) at least one herbicide selected from 5 Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl C) at least one more herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox, Chlorimuron Ethyl and Fluthiacet methylwith one or more inactive excipients effective for controlling or killing of resistant and tough 10 to control weeds.
An herbicidal synergistic composition of present invention controls all kind of monocots, dicots and sedges weeds. The most common weeds controlled are selected from Abutilon indicum, Acalypha indica, Acanthospermum hispidum, 15 Achyranthes aspera, Aerva tomentosa, Ageratum conyzoides, Alhagi camelorum,
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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, 5 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 10 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, 15 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, Marsilea quadrifoliata, Medicago denticulate, Mimosa pudica, Melilotus alba, Melilotus indica, Ocimum canum, Oenothera biennis, 20 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, 25 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. 30 In one embodiment of the present invention, the synergistic herbicidal composition of present invention is effective in controlling the growth of
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undesirable vegetation, e.g., in monocot and dicot crops including genetically modified and conventional or non-genetically modified varieties of Soybean (Glycin max), Peanut (Arachis hypogaea), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), French bean (Phaseolus vulgaris), Indian bean (Lablab 5 purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Cotton (Gossypium spp.), Sugarcane (Saccharum officinarum) , Castor (Ricinus communis), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus 10 esculentus) , Tomato (Solanum lycopersicun) , Chilly (Capsicum annum). The synergistic herbicidal compositions can be also employed to promote non-selection and selective herbicidal action in fallow land, non-cropped industrial land, road and highway sides. 15
The present invention of synergistic herbicidal composition comprising A) Cycloxydim B) at least one herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl C) at least one more herbicide 20 selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox, Chlorimuron Ethyl and Fluthiacet methyl with one or more inactive excipients has advantages as mentioned below; 1. Synergism between three active ingredients in comparison to activity of single ingredients, combination of two active ingredients. Wherein the 25 present invention having synergism and thereby reduces the total quantity of active ingredient loading in to the environment. 2. Covers broad spectrum of weeds 3. Synergism will be useful for control/kill of resistant and tough to control weeds. 30 4. Offer longer residual control
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Application Time and Method: The synergistic herbicidal composition can be applied as foliar spray as pre emergence, Early post emergence or late post emergence. It can be also applied as blanket spray over the crop and weed or in between the rows as directed 5 application. The present compositions can be applied to weeds or their locus by the use of conventional ground or aerial duster, sprayers, and granules applicators by addition to irrigation and by other conventional means known to those skilled in art.
10 One or more inactive excipient is selected from including but not limited to dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent. 15 Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or stearic barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersants are sodium lignosulphonates. For suspension concentrates, very good 20 adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of 25 very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points 30 onto the particle surfaces. Examples of dispersants used herein include but not
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limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.
5 Anti-freezing agent as used herein can be selected from the group consisting of polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol.
Water-based formulations often cause foam during mixing operations in 10 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. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, 15 or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.
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 20 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 25 powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates and the salts thereof which are standard in agricultureor 30 mixtures thereof.
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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 treated. The carrier may be solid (clays, natural or synthetic silicates, 5 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). 10 Biocides / Microorganisms cause spoilage of formulated products. Therefore anti-microbial agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such 15 as sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxy benzoates or mixtures thereof. Thickeners or gelling agents are used mainly in the formulation of suspension 20 concentrates, emulsions and suspo-emulsions 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 25 clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, 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 30 thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose;
Page 18 of 40
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.
The quick coating agent can be a conventionally available sticker, for example 5 polyesters, polyamides, poly- carbonates, polyurea and polyurethanes, acrylate polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, vinylalcohol, vinylacetate and vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymersand mixtures 10 thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, 15 poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), alkyd resins, and mixtures of two or more of these. Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an 20 application environment. Examples of biodegradable polymers that are useful in the present invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch esteraliphatic polyester blends, modified corn starch, 25 polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.
Buffering agent as used herein is selected from group consisting of calcium 30 hydroxyapatite, Potassium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate,
Page 19 of 40
calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.
The solvent for the formulation of the present invention may include water, water-soluble alcohols and dihydroxy alcohol ethers. The water-soluble alcohol 5 which can be used in the present invention may be lower alcohols or water-soluble macromolecular alcohols. The term "lower alcohol", as used herein, represents an alcohol having 1-4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. Macromolecular alcohol is not limited, as long as it may be dissolved in water in a suitable amount range, 10 polyethylene glycol, sorbitol, glucitol, etc. The examples of suitable dihydroxy alcohol ethers used in the present invention may be dihydroxy alcohol alkyl ethers or dihydroxy alcohol aryl ethers. The examples of dihydroxy alcohol alkyl ether include ethylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol 15 ethyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, dipropylene glycol ethyl ether, etc. The examples of dihydroxy alcohol aryl ethers include ethylene glycol phenyl ether, diethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, and the like. Any of the above mentioned solvent can be used either alone or in combination 20 thereof.
EXAMPLES
The present invention will now be explained in detail by reference to the 25 following formulation examples and a test example, which should not be construed as limiting the scope of the present invention.
Page 20 of 40
Example 1: Emulsifiable Concentrate (EC) formulation of Cycloxydim 5% + Clodinafop Propargyl 5% + Sodium Acifluorfen 16%
Ingredients
%
Cycloxydim A.I.
5.00
Clodinafop Propargyl A.I.
5.00
Cloquintocet mexyl safener A.I.
1.25
Sodium Acifluorfen A.I.
16.00
Calcium dodecylBenzene sulfonate
4.50
Tristryryle Phenol Ethoxylates
4.50
Alkyl Polyethylene Glycol Ether
1.00
NMP
8.00
Solvent C-IX
q.s.
Total
100.00
5
Process for preparation of Emulsifiable Concentrate (EC) formulation
Step 1
Charge half quantity of solvent and then mix the technical into this solvent until 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 required pack sizes.
Example 2: Emulsifiable Concentrate (EC) formulation of Cycloxydim 5% + Clodinafop Propargyl 5% + Sodium Fomesafen 16%
10
Ingredients
%
Cycloxydim A.I.
5.00
Clodinafop Propargyl A.I.
5.00
Cloquintocet mexyl safener A.I.
1.25
Sodium Fomesafen A.I.
16.00
Calcium dodecylBenzene sulfonate
4.50
Tristryryle Phenol Ethoxylates
5.50
Alkyl Polyethylene Glycol Ether
1.00
NMP
8.00
Solvent C-IX
q.s.
Total
100.00
Page 21 of 40
Procedure: as per Example 1
Example 3: Emulsifiable Concentrate (EC) formulation of Cycloxydim 3% + Quizalofop-p-ethyl 4% + Sodium Acifluorfen 16% 5
Ingredients
%
Cycloxydim A.I.
3.00
Quizalofop-P-Ethyl A.I.
4.00
Sodium Acifluorfen A.I.
16.00
Calcium dodecylBenzene sulfonate
4.50
Tristryryle Phenol Ethoxylates
5.50
Alkyl Polyethylene Glycol Ether
1.00
NMP
8.00
Solvent C-IX
q.s.
Total
100.00
Example 4: Emulsifiable Concentrate (EC) formulation of Cycloxydim 3% + Quizalofop-p-ethyl 4% + Sodium Fomesafen 16%
10
Ingredients
%
Cycloxydim A.I.
3.00
Quizalofop-P-Ethyl A.I.
4.00
Sodium Fomesafen A.I.
16.00
Calcium dodecylBenzene sulfonate
4.50
Tristryryle Phenol Ethoxylates
5.50
Alkyl Polyethylene Glycol Ether
1.00
NMP
8.00
Solvent C-IX
q.s.
Total
100.00
Procedure: as per Example 1
Example 5: Emulsifiable Concentrate (EC) formulation of Cycloxydim 3% 15 + Propaquizafop 4% + Sodium Acifluorfen 16%
Page 22 of 40
Ingredients
%
Cycloxydim A.I.
3.00
Propaquizafop A.I.
4.00
Sodium Acifluorfen A.I.
16.00
Calcium dodecylBenzene sulfonate
4.80
Tristryryle Phenol Ethoxylates
5.30
Alkyl Polyethylene Glycol Ether
1.00
NMP
8.00
Solvent C-IX
q.s.
Total
100.00 Procedure: as per Example 1
Example 6: Emulsifiable Concentrate (EC) formulation of Cycloxydim 3% + Propaquizafop 4% + Sodium Fomesafen 16% 5
Ingredients
%
Cycloxydim A.I.
3.00
Propaquizafop A.I.
4.00
Sodium Fomesafen A.I.
16.00
Calcium dodecylBenzene sulfonate
5.00
Tristryryle Phenol Ethoxylates
5.00
Alkyl Polyethylene Glycol Ether
1.00
NMP
8.00
Solvent C-IX
q.s.
Total
100.00
Procedure: as per Example 1
Example 7: Microemulsion (ME) formulation of Cycloxydim 2% + 10 Clodinafop Propargyl 1% + Imazethapyr 3.75%
Ingredients
%
Cycloxydim A.I.
2.00
Clodinafop Propargyl A.I.
1.00
Cloquintocet mexyl safener A.I.
0.25
Imazethapyr A.I.
3.75
Page 23 of 40
N-Methyl-2-pyrrolidone
15.00
Tristyryl Phenol Ethoxylates
12.00
Polyalkoxylated Butyl Ether
10.00
PolyEthyene Glycol
6.00
Silicon Based Antifoam
0.50
Benzisothiazolinone
0.30
D.M. Water
q.s.
Total
100.00
Process of preparation of Microemulsion (ME) formulation
Step 1
Aqueous phase:Charge 90% of total quantity of water in a vessel and then add preservative, Anti-freezing agent and antifoam and stirr well till clear solution.
Step 2
Organic Phase: In other vessel add solvent and technicals and then recommended surfactant slowly and mix completely under stirring.
Step 3
Now under moderate stirring add this oil phase into aqueous phase and let mix till completely homogeneous.
Step 4
Add the remaining amount of water and mix until homogeneous.
Step 5
Filter through a 50 mesh into an appropriate container.
Step 6
Final product is sent for QC approval.
Step 7
After approval material is packed in required pack sizes.
Example 8: Microemulsion (ME) formulation of Cycloxydim 1.5% + 5 Propaquizafop 2% + Imazethapyr 3.75%
Ingredients
%
Cycloxydim A.I.
1.50
Propaquizafop A.I.
2.00
Imazethapyr A.I.
3.75
N-Methyl-2-pyrrolidone
15.00
Tristyryl Phenol Ethoxylates
12.50
Polyalkoxylated Butyl Ether
9.50
PolyEthyene Glycol
6.00
Silicon Based Antifoam
0.50
Benzisothiazolinone
0.30
D.M. Water
q.s.
Total
100.00
Page 24 of 40
Procedure: as per Example 7
Lists of Preferred formulations
Sr No
active ingredient 1
active ingredient 2
active ingredient 3
active ingredients in %
Formulation Strength (%)
Formulation Type
Application Rate (g per hectare)
g.a.i per hectare
a.i.1
a.i.2
a.i.3
a.i.1
a.i.2
a.i.3
8
a.i.1
a.i.2(a)
a.i.3(a)
5
5
16
26
EC
1000
50.00
50.00
160.00
9
a.i.1
a.i.2(a)
a.i.3(a)
5
5
16
26
OD
1000
50.00
50.00
160.00
10
a.i.1
a.i.2(a)
a.i.3(f)
5
5
16
26
EC
1000
50.00
50.00
160.00
11
a.i.1
a.i.2(a)
a.i.3(f)
5
5
16
26
OD
1000
50.00
50.00
160.00
12
a.i.1
a.i.2(a)
a.i.3(g)
5
5
16
26
EC
1000
50.00
50.00
160.00
13
a.i.1
a.i.2(a)
a.i.3(g)
5
5
16
26
OD
1000
50.00
50.00
160.00
14
a.i.1
a.i.2(a)
a.i.3(b)
2
2
30
34
EC
2500
50.00
50.00
750.00
15
a.i.1
a.i.2(a)
a.i.3(b)
2
2
30
34
OD
2500
50.00
50.00
750.00
16
a.i.1
a.i.2(a)
a.i.3(c)
2
1
3.75
6.75
ME
2000
40.00
20.00
75.00
17
a.i.1
a.i.2(a)
a.i.3(c)
20
10
37.5
67.5
WG
200
40.00
20.00
75.00
18
a.i.1
a.i.2(a)
a.i.3(c)
8
4
15
27
SC
500
40.00
20.00
75.00
19
a.i.1
a.i.2(a)
a.i.3(d)
2
1
3.75
6.75
ME
2000
40.00
20.00
75.00
20
a.i.1
a.i.2(a)
a.i.3(d)
20
10
37.5
67.5
WG
200
40.00
20.00
75.00
21
a.i.1
a.i.2(a)
a.i.3(d)
8
4
15
27
SC
500
40.00
20.00
75.00
22
a.i.1
a.i.2(a)
a.i.3(e)
20
20
3.6
43.6
WG
250
50.00
50.00
9.00
23
a.i.1
a.i.2(a)
a.i.3(e)
20
20
3.6
43.6
WP
250
50.00
50.00
9.00
24
a.i.1
a.i.2(a)
a.i.3(e)
10
10
1.8
21.8
SC
500
50.00
50.00
9.00
25
a.i.1
a.i.2(b)
a.i.3(a)
3
4
16
23
EC
1000
30.00
40.00
160.00
26
a.i.1
a.i.2(b)
a.i.3(a)
3
4
16
23
OD
1000
30.00
40.00
160.00
27
a.i.1
a.i.2(b)
a.i.3(f)
3
4
16
23
EC
1000
30.00
40.00
160.00
28
a.i.1
a.i.2(b)
a.i.3(f)
3
4
16
23
OD
1000
30.00
40.00
160.00
29
a.i.1
a.i.2(b)
a.i.3(g)
3
4
16
23
EC
1000
30.00
40.00
160.00
30
a.i.1
a.i.2(b)
a.i.3(g)
3
4
16
23
OD
1000
30.00
40.00
160.00
31
a.i.1
a.i.2(b)
a.i.3(b)
1.2
1.6
30
32.8
EC
2500
30.00
40.00
750.00
32
a.i.1
a.i.2(b)
a.i.3(b)
1.2
1.6
30
32.8
OD
2500
30.00
40.00
750.00
33
a.i.1
a.i.2(b)
a.i.3(c)
1.5
2
3.75
7.25
ME
2000
30.00
40.00
75.00
34
a.i.1
a.i.2(b)
a.i.3(c)
15
20
37.
72.5
WG
200
30.00
40.00
75.00
Page 25 of 40
5
35
a.i.1
a.i.2(b)
a.i.3(c)
6
8
15
29
SC
500
30.00
40.00
75.00
36
a.i.1
a.i.2(b)
a.i.3(d)
1.5
2
3.75
7.25
ME
2000
30.00
40.00
75.00
37
a.i.1
a.i.2(b)
a.i.3(d)
15
20
37.5
72.5
WG
200
30.00
40.00
75.00
38
a.i.1
a.i.2(b)
a.i.3(d)
6
8
15
29
SC
500
30.00
40.00
75.00
39
a.i.1
a.i.2(b)
a.i.3(e)
16
16
3.6
35.6
WG
250
40.00
40.00
9.00
40
a.i.1
a.i.2(b)
a.i.3(e)
16
16
3.6
35.6
WP
250
40.00
40.00
9.00
41
a.i.1
a.i.2(b)
a.i.3(e)
8
8
1.8
17.8
SC
500
40.00
40.00
9.00
42
a.i.1
a.i.2(c)
a.i.3(a)
3
4
16
23
EC
1000
30.00
40.00
160.00
43
a.i.1
a.i.2(c)
a.i.3(a)
3
4
16
23
OD
1000
30.00
40.00
160.00
44
a.i.1
a.i.2(c)
a.i.3(f)
3
4
16
23
EC
1000
30.00
40.00
160.00
45
a.i.1
a.i.2(c)
a.i.3(f)
3
4
16
23
OD
1000
30.00
40.00
160.00
46
a.i.1
a.i.2(c)
a.i.3(g)
3
4
16
23
EC
1000
30.00
40.00
160.00
47
a.i.1
a.i.2(c)
a.i.3(g)
3
4
16
23
OD
1000
30.00
40.00
160.00
48
a.i.1
a.i.2(c)
a.i.3(b)
1.2
1.6
30
32.8
EC
2500
30.00
40.00
750.00
49
a.i.1
a.i.2(c)
a.i.3(b)
1.2
1.6
30
32.8
OD
2500
30.00
40.00
750.00
50
a.i.1
a.i.2(c)
a.i.3(c)
1.5
2
3.75
7.25
ME
2000
30.00
40.00
75.00
51
a.i.1
a.i.2(c)
a.i.3(c)
15
20
37.5
72.5
WG
200
30.00
40.00
75.00
52
a.i.1
a.i.2(c)
a.i.3(c)
6
8
15
29
SC
500
30.00
40.00
75.00
53
a.i.1
a.i.2(c)
a.i.3(d)
1.5
2
3.75
7.25
ME
2000
30.00
40.00
75.00
54
a.i.1
a.i.2(c)
a.i.3(d)
16
20
37.5
73.5
WG
200
32.00
40.00
75.00
55
a.i.1
a.i.2(c)
a.i.3(d)
6
8
15
29
SC
500
30.00
40.00
75.00
56
a.i.1
a.i.2(c)
a.i.3(e)
12
16
3.6
31.6
WG
250
30.00
40.00
9.00
57
a.i.1
a.i.2(c)
a.i.3(e)
12
16
3.6
31.6
WP
250
30.00
40.00
9.00
58
a.i.1
a.i.2(c)
a.i.3(e)
6
8
1.8
15.8
SC
500
30.00
40.00
9.00
[a.i.1=ycloxydim; a.i.2(a)=Clodinafop Propargyl; a.i.2(b)=Quizalofop-P-Ethyl; a.i.2(c)=Propaquizafop; a.i.3(a)=Sodium Acifluorfen; a.i.3(b)=Bentazon; a.i.3(c)=Imazethapyr; a.i.3(d)=Imazamox; a.i.3(e)=Chlorimuron Ethyl; a.i.3(f)=Sodium Fomesafen; a.i.3(g)=Sodium Lactofen]
Biological Example 5
The synergistic pesticide action of the inventive mixtures can be demonstrated by the experiments below. A synergistic effect exists wherever the action of a combination (ready-mix) 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 10
Page 26 of 40
that exhibits greater pesticide activity than the sum of the pesticide activities of the individual components. In the field of agriculture, it is often understood that the term “synergy” is as defined by Colby S.R. in an article entitled “ Calculation of the synergistic and antagonistic responses of herbicide combinations” published in the journal Weeds, 1967, 15, p.20-22, incorporated 5 herein by reference in its entirety. The action expected for a given combination of two active components can be calculated as follows:
Colby’s Formula:
The field experiments on present invention concerns a synergistic herbicidal 10 mixture comprising of cycloxydim, one more herbicide selected from the group of Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop, Haloxyfop-R-Methyl and one more herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyra, Imazamox, Chlorimuron Ethyl, Fluthiacet methyl were 15 carried out to evaluate the bioefficacy against different weed flora and phyto-toxicity in various crops, like soybean, black gram, cluster bean and groundnut.
Biological Example 1 : Synergistic weed control in Soybean, Glycine max
The field experiment were conducted in Soybean and the experimental details are 20 as below :
Crops & Varieties: Soybean (JS 335)
Experimental design: Randomized block design (R.B.D)
Replications: Four
No. of Treatments: As per treatment details 25
Page 27 of 40
Plot size: 30 sq. mt.
Application Time: 20 DAS (Days after sowing)
Observations: at 3, 7, 14 and 21 DAA (Days after Application)
Spray Volume: 375 liter water per hectare
Application Equipment: Manually operated knapsack sprayer fitted with flat fat 5 nozzle
Experiment method: The trials were laid out in Randomized Block design (RBD) with twelve (12) treatments, replicated four times. For each treatment plot size of 30 sq. mt. was maintained. To raise the crops all the agronomic practices 10 were followed as usually adopted. The treatments were applied as per the calculated dosages, using manually operated knap sack sprayer, fitted with flat fan nozzle. The spray volume was used at 375 l/ha for application of all herbicidal treatments. Species wise weed count recorded at 10 and 20 DAA (Days after Application) by using 0.25 m2 quadrant treatment wise in minimum 3 15 places randomly selected in the plot per replication. The species wise weed count further grouped in to Grasses and Broad Leaf weeds (BLW). The average of each variable was used together with the sum of all the variables per plot to calculate the percentage of control.
% Weed Control = 20
Mean weed count in untreated plot – Mean weed control in treated plot
1- ----------------------------------------------------------------------------------------- X 100
Mean weed count in untreated plot
The % weed control data used in Colby’s formula to calculate the synergism 25 between three herbicides.
Table 1: Treatment details
Treatment Details
Treatment Details
Formulation (ml or g per h)
Active Ingredient (g/h)
T1
Cycloxydim 20% EC+Clodinafop propargyl 15% WP+Acifluorfen Sodium 20% SL
250+333.33+750
50+50+150
Page 28 of 40
T2
Cycloxydim 20% EC+Clodinafop propargyl 15% WP+Fomesafen Sodium 24% SL
250+333.33+666.67
50+50+160
T3
Cycloxydim 20% EC+Clodinafop propargyl 15% WP
250+333.33
50+50
T4
Cycloxydim 20% EC+Acifluorfen Sodium 20% SL
250+750
50+150
T5
Cycloxydim 20% EC+Fomesafen Sodium 24% SL
250+666.67
50+160
T6
Clodinafop propargyl 15% WP+Acifluorfen Sodium 20% SL
333.33+750
50+150
T7
Clodinafop propargyl 15% WP+Fomesafen Sodium 24% SL
333.33+666.67
50+160
T8
Cycloxydim 20% EC
250.00
50
T9
Clodinafop propargyl 15% WP
333.33
50
T10
Acifluorfen sodium 20% SL
750.00
150
T11
Fomesafen sodium 24% SL
666.67
160
T12
Unweeded control
0
0
ml- milli liter, g- gram, h-hectare, DAA- Days After Application, EC Emulsifiable concentrate, SL Suspension Liquid, WP Wettable Powder
Table 2: Synergistic weed control in Soybean
Treatment Details
% Weed Control Observed
% Weed Control Expected
Colby Ratio o/e
10 DAA
20 DAA
10 DAA
20 DAA
10 DAA
20 DAA
T1
100.0
99.2
85.53
78.83
1.17
1.26
T2
100.0
98.8
85.31
78.64
1.17
1.26
T3
62.4
58.8
77.47
69.23
0.81
0.85
T4
70.2
62.2
70.60
62.99
0.99
0.99
T5
69.4
61.8
70.14
62.66
0.99
0.99
T6
67.8
59.8
68.41
60.65
0.99
0.99
T7
67.4
58.8
67.92
60.30
0.99
0.98
T8
54.2
46.2
T9
50.8
42.8
T10
35.8
31.2
T11
34.8
30.6
T12
0.0
0.0
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Weed flora composition- Grassy weeds (Echinochloa spp.,Dactyloctenium spp., Digitaria spp., Eleusine spp.) approx. 60% + Broad leaf weeds (Commelina spp., Euphoriba spp., Acalypha spp., Celosia spp., Digera spp.) approx. 40%
The Bioefficacy observations given in above (Table 2), shows that the inventive 5 mixture (T1 and T2) shows synergistic weed control (Colby ratio > 1) and provide excellent control of grasses and broad leaf weeds (BLW) compared to all prior art treatments as well as their solo application.
Biological Example 2 : Synergistic weed control in Black gram 10
Crop & Variety : Blackgram, LBG-787
Experimental design : Randomized block design (R.B.D)
Replications : Four
No. of Treatments : as given in the treatment details
Plot size : 30 sq. mt. 15
Application Time : 22 DAS (Days after sowing)
Observations : 15 DAA (Days after Application)
Spray Volume : 375 liter water per hectare
Application Equipment : Hand operated knapsack sprayer fitted with flat fan nozzle 20
Experiment method: as given in Biological Example 1
Table 3: Treatment details
Treatment Details
Treatment Details
Formulation (ml or g per h)
Active Ingredient (g/h)
T1
Cycloxydim 20% EC+Quizalofop-P-Ethyl 10% EC+Aciflurofen Sodium 20% SL
150+200+800
30+40+160
T2
Cycloxydim 20% EC+Quizalofop-P-Ethyl 10% EC+Fomesafen Sodium 24% SL
150+200+666.67
30+40+160
T3
Cycloxydim 20% EC+Quizalofop-P-Ethyl 10% EC
150+200
30+40
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T4
Cycloxydim 20% EC+Aciflurofen Sodium 20% SL
250+800
30+160
T5
Cycloxydim 20% EC+Fomesafen Sodium 24% SL
250+666.67
50+160
T6
Quizalofop-P-Ethyl 10% EC+Aciflurofen Sodium 20% SL
333.33+800
40+160
T7
Quizalofop-P-Ethyl 10% EC+Fomesafen Sodium 24% SL
333.33+666.67
40+160
T8
Cycloxydim 20% EC
150.00
30
T9
Quizalofop-P-Ethyl 10% EC
400.00
40
T10
Acifluorfen sodium 20% SL
800.00
160
T11
Fomesafen sodium 24% SL
666.67
160
T12
Unweeded control
0
0
ml- milli liter, g- gram, h-hectare, DAA- Days After Application, EC Emulsifiable concentrate, SL Suspension Liquid.
Table 4: Synergistic weed control in Blackgram
Treatment Details
% Weed Control Observed
% Weed Control Expected
Colby Ratio o/e
10 DAA
20 DAA
10 DAA
20 DAA
10 DAA
20 DAA
T1
100.0
98.6
87.93
84.45
1.14
1.17
T2
100.0
97.4
88.33
84.29
1.13
1.16
T3
82.8
77.6
83.61
79.43
0.99
0.98
T4
67.2
61.6
67.91
62.80
0.99
0.98
T5
68.6
62.0
68.96
62.41
0.99
0.99
T6
71.6
67.8
72.33
68.40
0.99
0.99
T7
72.4
67.6
73.23
68.06
0.99
0.99
T8
56.4
50.8
T9
62.4
58.2
T10
26.4
24.4
T11
28.8
23.6
T12
0.0
0.0
Weed flora composition- Grassy weeds (Brachiaria muticae, Echinochloa spp., 5 Eragrostis spp., Eleusine spp.) approx. 70% + Broad leaf weeds (Trianthema spp., Amaranthus spp., Commelina spp., ) approx. 30%
The Bioefficacy observations given in above (Table 2), shows that the inventive mixture (T1 and T2) shows synergistic weed control (Colby ratio > 1) and 10
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provide excellent control of grasses and broad leaf weeds (BLW) compared to all prior art treatments as well as their solo application.
Biological Example 3: Synergistic weed control in Groundnut
Crop & Variety : Groundnt, J-11 5
Experimental design : Randomized block design (R.B.D)
Replications : Four
No. of Treatments: Twelve
Plot size : 30 sq. mt.
Application Time : 18 DAS (Days after sowing) 10
Observations : 10 and 20 (Days after Application)
Spray Volume : 375 liter water per hectare
Application Equipment : Hand operated knapsack sprayer fitted with flat fan nozzle
Experiment method : as given in Biological example 1. 15
Table 5: Treatment details
Treatment Details
Treatment Details
Formulation (ml or g per h)
Active Ingredient (g/h)
T1
Cycloxydim 20% EC+Propaquizafop 10% EC+Aciflurofen Sodium 20% SL
150+200+800
30+40+160
T2
Cycloxydim 20% EC+Propaquizafop 10% EC+Fomesafen Sodium 24% SL
150+200+666.67
30+40+160
T3
Cycloxydim 20% EC+Propaquizafop 10% EC
150+200
30+40
T4
Cycloxydim 20% EC+Aciflurofen Sodium 20% SL
250+800
30+160
T5
Cycloxydim 20% EC+Fomesafen Sodium 24% SL
250+666.67
50+160
T6
Propaquizafop 10% EC+Aciflurofen Sodium 20% SL
333.33+800
40+160
Page 32 of 40
T7
Propaquizafop 10% EC+Fomesafen Sodium 24% SL
333.33+666.67
40+160
T8
Cycloxydim 20% EC
150.00
30
T9
Propaquizafop 10% EC
400.00
40
T10
Acifluorfen sodium 20% SL
800.00
160
T11
Fomesafen sodium 24% SL
666.67
160
T12
Unweeded control
0
0
ml- milli liter, g- gram, h-hectare, DAA- Days After Application, EC Emulsifiable concentrate, SL Suspension Liquid.
Table 6: Synergistic weed control in Groundnut
Treatment Details
% Weed Control Observed
% Weed Control Expected
Colby Ratio o/e
10 DAA
20 DAA
10 DAA
20 DAA
10 DAA
20 DAA
T1
95.8
91.4
85.61
80.94
1.12
1.13
T2
94.8
89.4
85.26
80.26
1.11
1.11
T3
60.2
58.6
77.73
71.73
0.77
0.82
T4
64.8
58.8
65.25
59.96
0.99
0.98
T5
63.8
57.6
64.38
58.54
0.99
0.98
T6
72.8
66.8
73.26
67.92
0.99
0.98
T7
71.8
65.8
72.59
66.78
0.99
0.99
T8
46.2
40.6
T9
58.6
52.4
T10
35.4
32.6
T11
33.8
30.2
T12
0.0
0.0
Weed flora composition- Grassy weeds (Echinochloa spp., Brachiaria muticae, 5 Dactyloctenium spp., Eleusine spp.,) approx. 60% + Broad leaf weeds (Commelina spp., Acalyphs spp., Phyllanthus spp.) approx. 40%
Observations on efficacy of tank mixes of Cycloxydim 20% EC+Propaquizafop 10% EC+Aciflurofen Sodium 20% SL and Cycloxydim 20% EC+Propaquizafop 10 10% EC+Fomesafen Sodium 24% SL shows synergism in terms of weed control of both the grassy and broad leaf weeds in groundnut crop.
All the above results show that the percentage of herbicidal control observed with tank mix combinations as were greater than the expected percentage (Colby 15
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Ration O/E) and thereby showing synergism in terms of weed control and duration of control.
Biological Example 3 : Phytotoxicity in soybean (Glycine max)
Soybean crop was raised as per the standard agronomic practices in the field to 5 conduct trials to assess phytotoxicity of inventive ready mixtures and prior art treatments given in Table 7. The trials were laid out in Randomized Block Design (RBD) with different treatments including untreated check (UTC), replicated four times. For each treatment plot size of 30 sq. mt was maintained. The application of different treatments with prescribed doses was done with manually operated 10 knapsack sprayer fitted with flat fan nozzle. The spray volume was used at 375 l/h for spraying. The Untreated check plot was sprayed with water alone. Observations on phytotoxicity viz., leaf scorching, leaf yellowing or any other visible symptoms were recorded at 3, 7, 15 and 21 days after spraying, by adopting 0-10 rating scale as below : 15
0= No phytotoxicity, 1 =1-10% leaf scorching/yellowing, 2=11-20% leaf scorching/yellowing… 9=81-90% leaf scorching/yellowing, 10=91-100% leaf scorching/yellowing.
Percent phytotoxicity was calculated by following formula: 20
Sum of all scores
% Phytotoxicity = ------------------------------------------------------------- X 100
Number of samples x highest rating scale
25
Table 7: Treatment details
Treatment No.
Treatment Details
Formulation (ml or g per h)
Active Ingredient (g/h)
T1 Cycloxydim 5% + Clodinafop Propargyl 5% + Sodium Acifluorfen 16% EC 1000
50+50+160
T2 Cycloxydim 5% + Clodinafop Propargyl 5% + Sodium Fomesafen 16% EC 1000
50+50+160
T3 Cycloxydim 3% + Quizalofop-p-ethyl 4% + 1000
30+40+160
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Sodium Acifluorfen 16% EC
T4 Cycloxydim 3% + Quizalofop-p-ethyl 4% + Sodium Fomesafen 16% EC 1000
30+40+160
T5 Cycloxydim 3% + Propaquizafop 4% + Sodium Acifluorfen 16% EC 1000
30+40+160
T6 Cycloxydim 3% + Propaquizafop 4% + Sodium Fomesafen 16% EC 1000
30+40+160
T7 Cycloxydim 2% + Clodinafop Propargyl 1% + Imazethapyr 3.75% ME 2000
40+20+75
T8 Cycloxydim 1.5% + Propaquizafop 2% + Imazethapyr 3.75% ME 2000
40+20+75
T9
Untreated Control (UTC) water spray only
-
-
Table 8: Phytotoxicity observations on soybean
Treatment No.
Leaf schorching (%)
1 DAA
3 DAA
7 DAA
10 DAA
15 DAA
20 DAA
T1
5.0
10.0
5.0
0.0
0.0
0.0
T2
5.0
10.0
5.0
0.0
0.0
0.0
T3
5.0
10.0
5.0
0.0
0.0
0.0
T4
5.0
10.0
5.0
0.0
0.0
0.0
T5
5.0
10.0
5.0
0.0
0.0
0.0
T6
5.0
10.0
5.0
0.0
0.0
0.0
T7
5.0
10.0
5.0
0.0
0.0
0.0
T8
5.0
10.0
5.0
0.0
0.0
0.0
T9
0.0
0.0
0.0
0.0
0.0
0.0
The phytotoxicity observations given in above (Table 8), shows all the inventive mixture were shows 5 to 10% leaf scorching which appeared after 24 hrs. of 5 spray and completely recovered by 10 days after application and does not cause any significant damage to the crop. ,CLAIMS:CLAIMS We claim; [CLAIM 1]. An synergistic herbicidal composition comprising component A) Cycloxydim; component B) herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl; component C) herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox,Chlorimuron Ethyl and Fluthiacet methyl; and D) one or more other inactive excipients. [CLAIM 2]. The synergistic composition as claimed in claim 1 wherein the component (A) Cycloxydim is in ratio of 0.1-25%, component (B) herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl is in ratio of 0.1 to 25% and component (C) herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox,Chlorimuron Ethyl and Fluthiacet methyl in ratio of 0.1 to 50%. [CLAIM 3]. The synergistic composition as claimed in claim 1 or 2, wherein inactive excipients are selected from the group consisting of dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent, binders and buffering agent. [CLAIM 4]. The synergistic composition as claimed in claim 1-3, wherein the formulations comprises of Suspension Concentrate (SC), Suspo emulsion (SE), Micro Emulsion (ME),Capsule Suspension (CS), Oil Dispersion (OD), mixed formulation of CS and SC (ZC), a
Page 36 of 40
mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW), Water Soluble Granules (SG), Water dispersible granule (WDG or WG), Water soluble bag formulation, Wettable Powder (WP), Soluble Powder (SP). [CLAIM 5]. The formulation comprising the synergistic composition as claimed in claim 1 or 4, wherein the Emulsifiable Concentrate (EC) formulation comprises: a) component (A) Cycloxydim is in ratio of 0.1-25%, component (B) herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl is in ratio of 0.1 to 25% and component (C) herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox,Chlorimuron Ethyl and Fluthiacet methyl in ratio of 0.1 to 50%; b) Cloquintocet mexyl safener c) Calcium dodecylBenzene sulfonate d) Tristryryle Phenol Ethoxylates e) Alkyl Polyethylene Glycol Ether f) NMP g) Solvent C-IX. [CLAIM 6]. The formulation comprising the synergistic composition as claimed in claim 1 or 4, wherein the Microemulsion (ME) formulation comprises: a) component (A) Cycloxydim is in ratio of 0.1-25%, component (B) herbicide selected from Clodinafop Propargyl, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, Fenoxaprop-P-Ethyl, Fluazifop-P-Butyl, Propaquizafop and Haloxyfop-R-Methyl is in ratio of 0.1 to 25% and
Page 37 of 40
component (C) herbicide selected from Acifluorfen, Fomesafen, Lactofen, Bentazon, Imazethapyr, Imazamox,Chlorimuron Ethyl and Fluthiacet methyl in ratio of 0.1 to 50%; b) Cloquintocet mexyl safener c) N-Methyl-2-pyrrolidone d) Tristyryl Phenol Ethoxylates e) Polyalkoxylated Butyl Ether f) PolyEthyene Glycol g) Silicon Based Antifoam h) Benzisothiazolinone i) D.M. Water. [CLAIM 7]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition is to be used to weeds controlled are selected from 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
Page 38 of 40
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, 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. [CLAIM 8]. The synergistic composition as claimed in any of the preceding claims, wherein the said composition effective in controlling the growth of undesirable vegetation, e.g., in monocot and dicot crops including genetically modified and conventional or non genetically modified varieties of Soybean (Glycin max), Peanut (Arachis hypogaea), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna
Page 39 of 40
unguiculata), Redgram (Cajanus cajan), French bean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Lentils (Lens culinaris), Cotton (Gossypium spp.), Sugarcane (Saccharum officinarum) , Castor (Ricinus communis), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Tomato (Solanum lycopersicun) , Chilly (Capsicum annum)
Dated this 30th Day of July, 2019
Signature:
Name: Bhavik Patel
Applicant’s Agent: IN/PA-1379
INFINVENT IP