[go: up one dir, main page]

WO2010143205A2 - Herbicidal composition - Google Patents

Herbicidal composition Download PDF

Info

Publication number
WO2010143205A2
WO2010143205A2 PCT/IN2010/000396 IN2010000396W WO2010143205A2 WO 2010143205 A2 WO2010143205 A2 WO 2010143205A2 IN 2010000396 W IN2010000396 W IN 2010000396W WO 2010143205 A2 WO2010143205 A2 WO 2010143205A2
Authority
WO
WIPO (PCT)
Prior art keywords
sodium
composition
weight
organic solvent
amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IN2010/000396
Other languages
French (fr)
Other versions
WO2010143205A4 (en
WO2010143205A3 (en
Inventor
Jaidev Rajnikant Shroff
Vikram Rajnikant Shroff
Ashim Kumar Dutta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UPL Ltd
Original Assignee
United Phosphorus Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by United Phosphorus Ltd filed Critical United Phosphorus Ltd
Priority to CN201080035114.XA priority Critical patent/CN102458131B/en
Publication of WO2010143205A2 publication Critical patent/WO2010143205A2/en
Publication of WO2010143205A3 publication Critical patent/WO2010143205A3/en
Publication of WO2010143205A4 publication Critical patent/WO2010143205A4/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/48—Nitro-carboxylic acids; Derivatives thereof

Definitions

  • the present invention relates to herbicidal formulations comprising acifiuorfen sodium.
  • Selective herbicides kill specific targets while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of the weed and are often synthetic "imitations" of plant hormones.
  • Herbicides used to clear waste ground, industrial sites, railways and railway embankments are non-selective and kill all plant material with which they come into contact.
  • Phytotoxic means harmful or lethal to plants. Phytotoxicity is the degree to which a chemical or other compound is toxic to plants. Phytotoxic effects caused by herbicides can be from spray droplets, soil residues or vapors contacting sensitive plants. Plants can also be harmed by herbicides which move off target in water or soil or when sensitive crops are planted in fields too soon after a herbicide treatment was applied for a previous crop.
  • Phytotoxic effects ranges from slight burning or browning of leaves to death of the plant. Sometimes the damage appears as leaf cupping, crinkling and speckling, distorted leaves, fruit, flowers or stems. Damage symptoms vary with the herbicide and the type of plant that has been affected.
  • US Patent 4 063 929 discloses, novel diphenyl ether herbicides including Acifluorfen acid, 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid, and its agrochemically acceptable salts.
  • Acifluorfen sodium is a selective contact diphenyl ether herbicide, which exhibits both pre and post-emergence weed control.
  • This herbicide is effective for control of broad leaved weeds with some effects on grasses in soybeans, peanuts, peas and rice. Despite being a selective herbicide, its phyototoxic action or phytotoxicity on desired crop is reported in the literature.
  • Acifluorfen exerts its major effects through toxic products formed following light activation, lipid peroxidation, activated by photosynthetic electron transport and tetrapyrrole accumulation, is among more recent explanations of phytotoxicity.
  • Acifluorfen affects growth and phenyl propanoid metabolism in soybean and spinach.
  • Acifluorfen sodium is formulated as Soluble Liquid (SL) formulation and is registered and marketed under the brand name of Blazer.
  • SL Soluble Liquid
  • Blazer ® Acifluorfen sodium soluble liquid formulation
  • the present invention provides such formulations of acifluorfen sodium that are non-phytotoxic.
  • Acifluorfen sodium is a selective contact diphenyl ether herbicide, which exhibits both pre and post-emergence weed control.
  • a common problem with selective herbicides is that its weed control spectrum, that is, the range of weed species effectively controlled by the herbicide, does not embrace the full diversity of weeds present in a crop. It has therefore been common to apply two or more herbicides simultaneously in order to achieve the desired spectrum of control.
  • United States Patent No. 4713109 teaches a 2-propynyl ester of the compound 2- (4- (3-Chloro-5-fluoro-2-pyridyloxy)-phenoxy-propionic acid, which is commonly known as clodinafop-propargyl, a compound possessing demonstrated herbicidal activity against grassy weeds in winter cereals specially in wheat and barley as well as pulses. It is a member of the oxy phenoxy acid ester class of herbicides. It is known that clodinafop propargyl interacts with and inhibits the acetyl co-enzyme A carboxylase, which is essential for the production of lipids or fatty acids needed for plant growth.
  • the selectivity of this herbicide is based on the difference in the speed of herbicide breakdown in the crop versus the weeds.
  • Clodinafop-propargyl converts from the ester form to the active acid and then to biologically inactive compounds.
  • Grass weeds such as wild oats and wild millet cannot effectively break down clodinafop-propargyl, so they are controlled as a lethal dose accumulates at the meristematic growing points. This is a post emergence, selective systemic grass herbicide and is known to control grasses such as green foxtail, barnyard grass,
  • Herbicide combinations offer advantages of improved weed control, a greater spectrum of weeds controlled, reduced cost and reduced residue problems.
  • the present invention also provides such a synergistic herbicidal composition of clodinafop-propargyl and acifluorfen sodium.
  • clodinafop-propargyl undergoes hydrolysis in the presence of an aqueous medium in acidic environment rendering it incapable of being formulated as stable formulation along with acifluorfen sodium or fomesafen sodium as a stable soluble liquid formulation.
  • US Patent 4285723 discloses, selective diphenyl ether herbicides including fomesafen, 5-(2-chloro- ⁇ , ⁇ , ⁇ -trifiuoro-/?-tolyloxy)-N-mesyl-2- nitrobenzenecarboximidate, and its agrochemically acceptable salts.
  • Fomesafen sodium is a selective early post emergent herbicide used to control broad leaved weeds in soybean.
  • US Patent No. 6369001 provides a liquid concentrate herbicidal microemulsion composition comprising water; a water-soluble herbicide and an oil-soluble cyclohexenone or aryloxyphenoxypropionate graminicide.
  • This patent discloses many examples of water soluble herbicide such as acifluorfen and fomesafen and oil soluble cyclohexenone such as Clodinafop-propargyl. However, it does not teach the selective combinations of acifluorfen sodium or fomesafen sodium and Clodinafop propargyl. Further, this patent does not address and solve the specific degradation problem of Clodinafop- propargyl, particularly in an aqueous environment. It was found that liquid concentrates or water based formulations comprising clodinafop- propargyl and acifluorfen sodium or fomesafen sodium have poor stability and aggravate the problem of degradation of clodinafop- propargyl.
  • Fomesafen sodium is formulated as Microemulsion (ME) and Soluble Liquid (SL) formulation. It is registered and marketed under the brand name of
  • the present inventors have also found that soluble liquid, wettable powder, water dispersible granules and also tank mixtures including acifluorfen sodium or fomesafen sodium with Clodinafop propargyl causes phytotoxicity on desired crops. Therefore, there is need in the art to provide a formulation of acifluorfen sodium or fomesafen sodium with Clodinafop propargyl that causes no phytotoxicity.
  • clodinafop- propargyl and acifluorfen sodium or fomesafen sodium that surprisingly meets the challenge of providing a storage stable formulation clodinafop- propargyl and acifluorfen sodium or fomesafen sodium which is also non phytotoxic.
  • no successful attempts have been made to formulate an emulsif ⁇ able concentrate of acifluorfen sodium or fomesafen sodium and clodinafop-propargyl.
  • the present invention provides such a storage stable agrochemical emulsifiable concentrate of clodinafop- propargyl and acifluorfen sodium or fomesafen sodium that causes no phytotoxicity.
  • the present invention at least achieves one of the following objectives.
  • Yet another object of the present invention is to provide a herbicidal emulsifiable concentrate comprising acifluorfen sodium and second herbicide selected from the class of aryloxyphenoxypropionates known as "fops" herbicide.
  • Yet another further object of the present invention is to provide a process for the preparation of a herbicidal emulsifiable concentrate comprising acifluorfen sodium.
  • It is further object of the present invention is to provide a synergistic herbicide composition exhibiting a broad spectrum of activity in controlling diversity of broad leaf weeds and grasses present in crops.
  • Another object of the present invention is to provide a synergistic herbicidal composition that enhances performance of weed control thereby reducing the required application frequency of the composition to control the grassy and broadleaved weeds in a crop field.
  • Further object of the present invention is to provide a storage stable agrochemical emulsifiable concentrate of clodinafop propargyl and acifluorfen sodium or fomesafen sodium.
  • a non phytotoxic herbicidal emulsif ⁇ able concentrate comprising an agrochemically effective amount of acifluorfen sodium.
  • a non phytotoxic herbicidal emulsifiable concentrate comprising; (i) an agrochemically effective amount of acifluorfen sodium;
  • ratio of the said first and second organic solvents is in the range from about 4: 1 to about 0.04: 1 by weight.
  • a non- phytotoxic emulsifiable concentrate comprising acifluorfen sodium in an amount of about 16.5 % by weight of the composition; an organic solvent having a dielectric constant of 18.2; another organic solvent having a dielectric constant of 2.5 wherein the ratio of said organic solvents is about 1.5: 1 by weight; an emulsifying agent or mixtures thereof in an amount of about 15 % by weight of the composition; and a stabilizer in an amount of about 1 % by weight of the composition.
  • a non phytotoxic herbicidal emulsifiable concentrate comprising an agrochemically effective amount of acifluorfen sodium and an agrochemically effective amount of a second herbicide selected from the class of aryloxyphenoxypropionates.
  • a process for the preparation of a non phytotoxic herbicidal emulsifiable concentrate comprising: (a) admixing at least one organic solvent having a dielectric constant of from about 12 to about 50 and at least another organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; and (c) adding at least one emulsifying agent in an amount of from about 0.1 % to about 40 % and at least a stabilizer in an amount of from about 0.25 to about 10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture.
  • a synergistic herbicidal composition comprising an agrochemically effective amount of acifluorfen sodium; and an agrochemically effective amount of clodinafop propargyl.
  • a storage stable agrochemical emulsifiable concentrate comprising:
  • ratio of said first and second organic solvents is in the range from about
  • a storage stable agrochemical emulsifiable concentrate comprising acifluorfen sodium in an amount of about 16.5 % by weight of the composition, Clodinafop propargyl in an amount of about 8 % by weight of the composition, an organic solvent having a dielectric constant of 18.2, another organic solvent having a dielectric constant of 2.5; wherein the ratio of said organic solvents is about 2:1 by weight, an emulsifying agent or mixtures thereof in an amount of about 15 % by weight of the composition, and stabilizer in an amount of about 1 % by weight of the composition.
  • a process for the preparation of a storage stable agrochemical emulsif ⁇ able concentrate comprising the steps of (a) admixing at least one organic solvent having a dielectric constant of from about 12 to about 50 and at least another organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium or fomesafen sodium and an agrochemically effective amount of clodinafop propargyl to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; (c) adding at least one emulsifying agent in an amount of from about 0.1 % to about 40 % and at least a stabilizer in an amount of from about 0.25% to about
  • step (b) 10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture and; d) filtering the resultant mixture.
  • aqueous based formulations such as soluble liquid (SL) of acifluorfen sodium are phytotoxic.
  • SL soluble liquid
  • present inventors have also found that in addition to aqueous based formulations, wettable powder and water dispersible granules of acifluorfen sodium are also phytotoxic.
  • emulsifiable concentrates are suitable for limited number of active ingredients only. Many active ingredients are not soluble enough to be supplied economically in this form. Hitherto, no attempts have been made in the prior art to prepare emulsifiable concentrate of acifluorfen sodium.
  • the present invention provides a non- phytotoxic herbicidal emulsifiable concentrate comprising an agrochemically effective amount of acifluorfen sodium.
  • agrochemically effective amount is that quantity of active agent, applied in any amount which will provide the required control of broad leaved weeds and grasses.
  • the particular amount is dependent upon many factors including, for example, the crop, weeds sought to be controlled and environmental conditions.
  • the selection of the proper quantity of active agent to be applied is within the expertise of one skilled in the art.
  • the agrochemically effective amount of acifluorfen sodium comprises from about 0.01% to about 40% and preferably from about 0.1% to about
  • acifluorfen sodium comprises from about 15.5% to about 30 % and more preferably about 16.5% of the total weight of the compositions according to the present invention.
  • organic solvents having dielectric constants in predetermined ranges when used in combination in a specific weight ratio played a major role in providing emulsifiable concentrate with desired emulsif ⁇ ability, solubility profile and stability.
  • the non-phytotoxic herbicidal emulsifiable concentrate of the present invention comprise further ingredients selected from an organic solvent having a dielectric constant from about 12 to about 50, another organic solvent having a dielectric constant from about 1 to about 4, an emulsifying agent, a stabilizer and the like.
  • a non phytotoxic herbicidal emulsifiable concentrate comprising; (i) an agrochemically effective amount of acifluorfen sodium; (ii) at least a first organic solvent having a dielectric constant of from about 12 to about 50; and (iii) at least a second organic solvent having a dielectric constant of from about 1 to about 4, wherein the ratio of the said organic solvents is in the range from about 4: 1 to about 0.04: 1 by weight.
  • the dielectric constant is denoted as ⁇ and dielectric constant of mixture of organic solvents having dielectric constants of from about 12 to about 50 and about 1 to about 4 is denoted as ⁇ m j X .
  • the organic solvent having a dielectric constant from about 12 to about 50 may be selected from the group comprising cyclohexanone, N-methyl pyrrolidone, dimethyl sulfoxide, acetophenone, dimethyl formamide, MIBK, butanol, isophorone, propanol, methanol, propargyl alcohol, acetone, acetonitrile, dichloromethane and the like.
  • the said solvent may be preferably selected from cyclohexanone, N-methyl pyrrolidone, dimethyl sulfoxide, acetophenone, dimethyl formamide, MIBK, butanol according to present invention. Still more preferably, said organic solvent is cyclohexanone.
  • the organic solvent having a dielectric constant of about 12 to about 50 comprises from about 4% to about 50% by weight of the composition, preferably from about 16 % to about 50 % by total weight of the composition according to the present invention.
  • said another organic solvent having a dielectric constant from about 1 to about 4 may be selected from toluene, xylene, solvesso- 200, C-9, solvesso- 100, solvesso- 150 and the like.
  • the preferred the organic solvent having a dielectric constant from about 1 to about 4 is xylene.
  • the organic solvent having a dielectric constant of from about 1 to about 4 comprises from about 4 % to about 40 % by weight of the composition, preferably from about 8 % to about 30% by total weight of the compositions according to the present invention.
  • the organic solvents having a dielectric constants of from about 12 to about 50 and from about 1 to about 4 together comprises from about 10% to about 70% by total weight of the composition.
  • the present invention comprises utilizing said first and second organic solvents within the present emulsifiable concentrate formulations in a weight ratio of from about 4: 1 to about 0.04 : 1.
  • the emulsifiable concentrate according to present invention provides best stability, emulsifiability and solubility when ⁇ m j X is from about 4 to about 35 and preferably when ⁇ m j X is from about 4 to about 23.
  • compositions according to the present invention comprise at least one emulsifying agent.
  • the emulsifying agent may be preferably selected from a group comprising lignosulphonates, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, non- ionic polyethoxylates, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, calcium salts of alkyl benzene
  • the emulsifying agent may be selected from a group comprising ethoxylated alkyl phenols, alkyl benzene sulfonates and calcium salts of alkyl benzene sulfonates.
  • the preferred emulsifying agent may also be selected from the group comprising nonyl phenol ethoxylate, styrenated phenol ethoxylate, castor oil ethoxylate, calcium dodecyl benzene sulphonate, sodium tetrapropylene benzenesulfonate, sodium 6- dodecylbenzenesulfonate and mixtures thereof.
  • the emulsifying agent is preferably used in an amount of about 0.1 to about 40.0 %,' and preferably from about 1.0 to about 30.0 % by total weight of the compositions according to the present invention. In another preferred embodiment, the emulsifying agent is present in an amount of about 2.0 to about 20.0 % by total weight of the compositions. In an embodiment, the compositions according to present invention additionally comprises stabilizer.
  • the stabilizer may be preferably selected from butanol, propanol, propargyl alcohol, acetic anhydride, acetic acid, epichlorohydrin and epoxidised soybean oil and like.
  • the stabilizer is preferably used in an amount of about 0.25% to about
  • the storage stability of the present emulsion concentrate is dependent, inter alia, on the pH of the final formulation.
  • the emulsifiable concentiate of the present invention affords excellent storage stability in a pH range of from about 4.0 to about 6.0.
  • the non phytotoxic herbicidal emulsifiable concentrate according to the present invention are prepared by a process comprising: (a) admixing at least a first organic solvent having a dielectric constant of from about 12 to about 50 and at least a second organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; and (c) adding at least one emulsifying agent in an amount of from about 0.1% to about 40% and additionally adding a stabilizer in an amount of from about 0.25 to about 10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture.
  • said process for the preparation of a non-phytotoxic herbicidal emulsifiable concentrate additionally comprises filtering the resultant mixture obtained in step (c) of the
  • the non-phytotoxic herbicidal emulsifiable concentrate comprising acifluorfen sodium further comprises a second herbicide selected from class of aryloxyphenoxypropionates, called as "fops".
  • the present invention provides a non- phytotoxic herbicidal emulsifiable concentrate comprising an agrochemically effective amount of acifluorfen sodium and a second herbicide selected from the class of aryloxyphenoxypropionates known as "fops" herbicide.
  • the "fops" herbicide comprises a herbicide selected from the group comprising clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, fluazifop-butyl, fluazifop-P-butyl, haloxyfop, propaquizafop, quizalofop and quizalofop-P.
  • "fops" herbicide comprises ' from about 0.1% to about 50%, preferably from about 1.0% to about 40% by total weight of the compositions according to the present invention. More preferably, said second herbicide comprises about 8% by total weight of the composition according to the present invention.
  • the non-phytotoxic herbicidal emulsifiable concentrate comprising an agrochemically effective amount of acifluorfen sodium and a second herbicide is prepared by the procedure described hereinabove.
  • acifluorfen sodium and clodinafop propargyl are synergistic and has broad spectrum of activity.
  • a person skilled in the art would not expect that selecting acifluorfen sodium from known diphenyl ether herbicides, known as "fen” herbicides and Clodinafop propargyl from aryloxyphenoxypropionates, known as
  • Herbicide combinations offer advantages of improved weed control, a greater spectrum of weeds controlled, reduced cost and reduced residue problems.
  • the underlying mechanism by which a combination of herbicides results in synergistic action is unknown to a person skilled in the art.
  • the present inventors set about providing a herbicidal composition that is synergistic.
  • the present invention provides a synergistic herbicidal composition
  • a synergistic herbicidal composition comprising an agrochemically effective amount of acifluorfen sod.ium; and an agrochemically effective amount of clodinafop propargyl.
  • clodinafop propargyl comprises from about 0.1% to about 50%, preferably from about 1.0% to about 40%, more preferably 2-10% by total weight of the compositions according to the present invention. Most preferably, clodinafop propargyl comprises about 8% by total weight of the composition according to the present invention.
  • the synergistic herbicidal compositions can be either solid or liquid formulations or solutions.
  • the herbicidal compositions of the present invention can be formulated as soluble liquid, water based emulsions, suspension concentrates, wettable powders, emulsifiable concentrates, dusts, water dispersible granules, aerosols, or flowable emulsion concentrates.
  • the compounds are extended with a liquid or solid carrier and, when desired, suitable surfactants are incorporated.
  • the synergistic compositions according to the present invention may be formulated as emulsifiable concentrates.
  • the synergistic herbicidal compositions of the present invention may include adjuvants, such as wetting agents, spreading agents, dispersing agents, stickers, adhesives, and the like, in accordance with agricultural practices and the formulation type.
  • adjuvants such as wetting agents, spreading agents, dispersing agents, stickers, adhesives, and the like.
  • the selection of the adjuvants according to the desired formulation type is within expertise of the person skilled in the art and is not particularly limiting.
  • the synergistic herbicidal compositions of the present invention can be prepared according the conventional procedure used for formulating desired formulation type and is within the expertise of the person skilled in the art.
  • the formulations comprising the synergistic combination of acifluorfen sodium and clodinafop propargyl may be formulated using the ingredients and the process for the preparation of non phytotoxic emulsifiable concentrate comprising acifluorfen sodium.
  • compositions according to the present invention optionally comprise a safener.
  • the safener is cloquintocet-mexyl that accelerates the rate of clodinafop-propargyl break down in crops, thus preventing the accumulation of a lethal dose.
  • the safener is present in an amount of about 0.1% to about 30% by weight of the second active ingredient component, preferably 1% to about 15% by weight of clodinafop acid or an agrochemically acceptable salt or an ester thereof.
  • soluble liquid or water based formulation comprising clodinafop propargyl and acifluorfen sodium or fomesafen sodium had poor stability.
  • the inventors conducted experiments on the soluble liquid formulations comprising these two active ingredients and observed that a soluble liquid composition comprising acifluorfen sodium or fomesafen sodium and clodinafop propargyl was highly unstable and quickly degraded rendering the composition incapable of being used.
  • clodinafop propargyl In order to solve the problem of water mediated degradation of clodinafop propargyl, it was essential to co-formulate clodinafop propargyl and acifluorfen sodium or fomesafen sodium wherein the use of aqueous phase is completely eliminated thereby solving the instability problem of clodinafop propargyl.
  • An emulsif ⁇ able concentrate is the example of such formulation type.
  • active ingredient is a water-soluble herbicide such as acifluorfen sodium or fomesafen sodium.
  • emulsif ⁇ able concentrates of water soluble active ingredients such as acifluorfen sodium or fomesafen sodium were difficult to formulate because of their low solubility in conventional non polar medium used for making emulsif ⁇ able concentrates. It is known in the art that emulsif ⁇ able concentrates are suitable for limited number of active ingredients only. Many active ingredients are not soluble enough to be supplied economically in this form.
  • aqueous formulation, wettable powder, water dispersible granules and the tank mixtures of acifluorfen sodium or fomesafen sodium and Clodinafop propargyl cause phytotoxicity to the desired crops.
  • emulsifiable concentrate formulation of acifluorfen sodium or fomesafen sodium with clodinafop propargyl solved the problem of phytotoxicity to the desired crops.
  • the present inventors set about providing a composition that is storage stable and non- phytotoxic.
  • the present invention provides a storage stable agrochemical emulsifiable concentrate comprising;
  • ratio of the said organic solvents is in the range from about 4: 1 to about 0.04: 1 by weight.
  • the preferred water soluble herbicide is fomesafen sodium, it is present in an amount of from about 4 % to about 8 % and preferably about 8.4 % of the total weight of the compositions according to the present invention.
  • the amount of clodinafop propargyl, the selection of preferred organic solvents and their respective percentages to achieve desirable properties of the end- formulation, the selection and amount of preferred emulsifying agents, the choice of suitable stabilizers, the preferred pH range, the selection of preferred safeners etc. are as per the preceding aspects and embodiments of the present invention, which are reproduced herein in its entirety.
  • the emulsifiable concentrate according to present invention provides best stability, emulsifiability and solubility when ⁇ n ,i X is from about 4 to about 35 and preferably when ⁇ ni j X is from about 4 to about 23.
  • ⁇ m j X of the selected ratio of solvents is not particularly limiting as long as the desired ratio of the solvents is maintained.
  • the emulsifiable concentrate formulations according to the present invention are prepared by a process comprising (a) admixing at least a first organic solvent having a dielectric constant of from about 12 to about 50 and at least a second organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium or fomesafen sodium and an agrochemically effective amount of clodinafop propargyl to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; (c) adding at least one emulsifying agent in an amount of from about 0.1% to about 40% and at least one stabilizer in an amount of from about 0.25% to about 10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture and; d) filtering the resultant mixture.
  • the formulations as described above have selective herbicidal action for crop plants and weeds. Such a selective herbicidal action renders the composition useful to control the following weeds.
  • Monocotyledon weeds or grassy weeds of the genera such as wild oats (Avena), crabgrass ⁇ Digitaria), barnyardgrass (Echinochloa), goosegrass (Eluesin), millet grass ⁇ Panicum), foxtail (Setaria.), bermudagrass (Cynodon), Blue grass (Poa), sorghum (sorghum), bulrush (Scripus), quackgrass (Agropyron) and arrow grass
  • Dicotyledon weeds or broad leaved weeds of the genera such as lambsquarters (Chenopodium), pigweeds (Amaranthus), purslane (Portulaca), morning glory (Ipomoea), nightshade (Solanum), spurge (Euphorbia), ragweed (Ambroasia), small melon (Cucumis), starbur (Acanthospermum), cocklebur (Xanthium),ground cherry (Physalis), annual nettle (Urtica), knotweed (Polygonum), speedwell (Veronica), thomapple (Datura), acalypha ⁇ Acalypha), Leucas, wild jute (Corchorus), Digera, Parthenium, Commelina, Celosia, Phyllanthus, Chrozophora, Ocimum, Grangia, Capsella, Vicia, Celoma, and Cyperus haspan.
  • the formulations of the present invention have a selective herbicidal action and may be used for post emergence weed control in various crops viz. Soybean, Green gram, Black gram, Groundnut, wheat and pea. Further, this composition may also be used as inter row directed application as post emergence weed control and pre planting application in case of zero tillage cultivation before planting of crop in some susceptible crops such as cotton, potato, tomato, chilli, sugarcane, onion, cucurbits, cabbage, cauliflower, beets (especially sugarbeets), sunflowers, rapeseeds and for achieving an effective weed control in perennial crops (grape vines and orchards).
  • some susceptible crops such as cotton, potato, tomato, chilli, sugarcane, onion, cucurbits, cabbage, cauliflower, beets (especially sugarbeets), sunflowers, rapeseeds and for achieving an effective weed control in perennial crops (grape vines and orchards).
  • the formulations of the present invention can be used as post emergence application to control wide range of weeds from weeds stage of 1 -2 leaf stage to 4 to 6 tilling/ branching stage, preferably 2 to 4 leaf stage or 7 to 60 days after sowing of crop, preferably 15 to 25 days after sowing of crop.
  • Example 1 Acifluorfen sodium 16.5 % w/w EC were prepared as follows:
  • Cyclohexanone and xylene were mixed in required quantity in a mixing vessel to form a first homogeneous mixture. Then required quantity of acifluorfen sodium was added at ambient temperature and stirred to form a second homogenous mixture. Calcium dodecyl benzene sulfonate and nonyl phenol ethoxylate and stabilizer were added to the second homogenous mixture with stirring to obtain a homogenous mixture, which was filtered to obtain the target emulsifiable concentrate.
  • Cyclohexanone and xylene were mixed in required quantity in a mixing vessel to form a first homogeneous mixture. Then required quantity of acifluorfen sodium and clodinafop propargyl wasadded at ambient temperature and stirred to form a second homogenous mixture. Calcium dodecyl benzene sulfonate and nonyl phenol ethoxylate and stabilizer were added to the second homogenous mixture with stirring to obtain a homogenous mixture and then filtered the resultant mixture.
  • Cyclohexanone and xylene were mixed in required quantity in a mixing vessel to form a first homogeneous mixture. Then required quantity of acifluorfen sodium and clodinafop propargyl wereadded at ambient temperature and stirred to form a second homogenous mixture. Calcium dodecyl benzene sulfonate and nonyl phenol ethoxylate and stabilizer wereadded to the second homogenous mixture with stirring to obtain a homogenous mixture and then filtered the resultant mixture.
  • Fomesafen sodium 8.4 % w/w and Clodinafop- propargyl 4.25 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 3.75:1 was prepared as per the process of Example 1.
  • Fomesafen sodium 5.6 % w/w and Clodinafop- propargyl 2.8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 3.89:1 was prepared as per the process of Example 1.
  • Fomesafen sodium 4.2 % w/w and Clodinafop- propargyl 2.12 % w/w EC including combination of cyclohexanone and toluene in a weight ratio of 3.68:1 was prepared as per the process of Example 1.
  • emulsifiable concentrates prepared as per the Examples 1 to 22 including combination of different organic solvents having dielectric constant between the specified ranges as discussed above and varied weight ratios were tested for storage stability, solubility and emulsifiability. It was observed that formulations prepared according to Examples 1-19 were stable and showed excellent solubility and emulsifiability whereas the formulations prepared as per the Examples 20-22 showed separation of emulsifiable concentrate on storage and therefore had poor stability.
  • the emulsifiable concentrates prepared for the purpose of experiment includes
  • Percent phytotoxicity was determined using the following formula.
  • E Expected % control by mixture of two products A and B in a defined dose.
  • Nozzle type Plat fan Table 2 Synergistic effect of combination of Acifluorfen sodium + Clodinafop propargyl against grassy and broad leaf weeds in Black gram
  • Tank mixture of acifluorfen sodium and clodinafop propargyl and ready mix of the acifluorfen sodium and Clodinafop propargyl in different formulation types was prepared as Example 1, Example 2, Example 3 and Example 4 as follows
  • Example 2 Example 3:
  • the crops considered for phytotoxicity evaluation was Soybean (Glycine max) and Black gram (Phaseolus mungo) Roxb) for test.
  • Tank mixture of acifluorfen sodium and Clodinafop propargyl and ready mix of the acifluorfen sodium and Clodinafop propargyl in different formulation types was prepared as Example 1, Example 2, Example 3 and Example 4 and phytotoxicity on test were compared through field trials.
  • the trial was laid out in Randomized Black Design (RBD) with nine treatments including untreated control, replicated three times for each example. For each treatments plot size of 24.5 sq.m was maintained. To raise the crops, all the agronomical practice was followed as usually adopted for soybean and black gram cultivation.
  • the test herbicidal compounds, with prescribed doses were applied using hand operated knapsack sprayer fitted plat fan nozzle. The spray volume was used at 500 //ha for application of all treatments.
  • Test -1 Comparison of phytotoxicity on soybean.
  • Test -2 Comparison of phytotoxicity on black gram.
  • Example 4 EC formulation according to the present invention was found to be safe for Soybean and Black gram crop and there was no adverse effect on crop.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The herbicidal formulation comprising acifluorfen sodium and processes for the preparation of same are disclosed. The present invention also discloses herbicidal formulation comprising acifluorfen sodium and a second active. The herbicidal formulations of the present invention are non phytotoxic and stable.

Description

HERBICIDAL COMPOSITION.
FIELD OF INVENTION
The present invention relates to herbicidal formulations comprising acifiuorfen sodium.
BACKGROUND OF THE INVENTION
The protection of crops from weeds and other vegetation which inhibit crop growth is a constantly recurring problem in agriculture. To help combat this problem, researchers in the field of synthetic chemistry have produced an extensive variety of chemicals and chemical formulations effective in the control of such unwanted growth. Chemical herbicides of many types have been disclosed in the literature and a large number are in commercial use.
Selective herbicides kill specific targets while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of the weed and are often synthetic "imitations" of plant hormones. Herbicides used to clear waste ground, industrial sites, railways and railway embankments are non-selective and kill all plant material with which they come into contact.
Unfortunately, many of such herbicides exhibit phytotoxicity to the desired crop as well as to the weeds or grasses sought to be controlled. Phytotoxic means harmful or lethal to plants. Phytotoxicity is the degree to which a chemical or other compound is toxic to plants. Phytotoxic effects caused by herbicides can be from spray droplets, soil residues or vapors contacting sensitive plants. Plants can also be harmed by herbicides which move off target in water or soil or when sensitive crops are planted in fields too soon after a herbicide treatment was applied for a previous crop.
Phytotoxic effects ranges from slight burning or browning of leaves to death of the plant. Sometimes the damage appears as leaf cupping, crinkling and speckling, distorted leaves, fruit, flowers or stems. Damage symptoms vary with the herbicide and the type of plant that has been affected.
US Patent 4 063 929 discloses, novel diphenyl ether herbicides including Acifluorfen acid, 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid, and its agrochemically acceptable salts. Acifluorfen sodium is a selective contact diphenyl ether herbicide, which exhibits both pre and post-emergence weed control.
This herbicide is effective for control of broad leaved weeds with some effects on grasses in soybeans, peanuts, peas and rice. Despite being a selective herbicide, its phyototoxic action or phytotoxicity on desired crop is reported in the literature.
An article in Journal of Agriculture and Food chemistry, 1983, 31(4), pp-751- 755 entitled "Acifluorfen increases the leaf content of phytoalexins and stress metabolites in several crops" teaches that leaves treated with acifluorfen sodium contain greatly increased levels of N-feruloyl- 3-methoxytyramine (spinach) and of 10 phytoalexins i.e. glyceollins I, II, and III and glyceofuran (soybean), phaseollin
(bean and pinto bean), pisatin (pea), medicarpin and wyerone (broad bean), xanthotoxin (celery), and hemigossypol (cotton). Enhanced synthesis of these compounds is related to acifluorfen concentration and exposure to light. The phytotoxicity of acifluorfen to spinach is counteracted by appropriate treatments with (aminooxy) acetic acid, L-2-(aminooxy)-3-phenylpropionic acid or silver nitrate and by heat shock. Under certain conditions soybean injury is ameliorated by combining (aminooxy) acetic acid with acifluorfen and silver nitrate with oxyfluorfen.
Weed Science, 1989, VoI 37: 743-747 entitled "Acifluorfen action on growth and phenolic metabolism in soybean (glycine max) seedlings, by Robert E" teaches that acifluorfen is a potent herbicide, but despite considerable studies to elucidate its mode of action, mechanism of its phytotoxicity is not fully understood. Light and oxygen are required for the development of maximal herbicidal symptoms of acifluorfen but photosynthesis is not involved. However, respiration and photosynthesis in soybean protoplasts and mitochondria are inhibited by low levels of acifluorfen. Acifluorfen exerts its major effects through toxic products formed following light activation, lipid peroxidation, activated by photosynthetic electron transport and tetrapyrrole accumulation, is among more recent explanations of phytotoxicity. Acifluorfen affects growth and phenyl propanoid metabolism in soybean and spinach.
Acifluorfen sodium is formulated as Soluble Liquid (SL) formulation and is registered and marketed under the brand name of Blazer. However, Acifluorfen sodium soluble liquid formulation (marketed as Blazer ®) is also known to produce phytotoxicity to desired crop. It shows the signs of phytotoxicity like leaf scorching, cupping, crinkling and speckling. Such damage affects the quality and overall yield of the desired crop.
Therefore, there is a long felt need in the art for acifluorfen sodium formulations that solves the problem of phytotoxicity. Hitherto, no attempts have been made to solve the phytotoxicity of acifluorfen sodium.
The present invention provides such formulations of acifluorfen sodium that are non-phytotoxic.
Further, Acifluorfen sodium is a selective contact diphenyl ether herbicide, which exhibits both pre and post-emergence weed control. A common problem with selective herbicides is that its weed control spectrum, that is, the range of weed species effectively controlled by the herbicide, does not embrace the full diversity of weeds present in a crop. It has therefore been common to apply two or more herbicides simultaneously in order to achieve the desired spectrum of control.
United States Patent No. 4713109 teaches a 2-propynyl ester of the compound 2- (4- (3-Chloro-5-fluoro-2-pyridyloxy)-phenoxy-propionic acid, which is commonly known as clodinafop-propargyl, a compound possessing demonstrated herbicidal activity against grassy weeds in winter cereals specially in wheat and barley as well as pulses. It is a member of the oxy phenoxy acid ester class of herbicides. It is known that clodinafop propargyl interacts with and inhibits the acetyl co-enzyme A carboxylase, which is essential for the production of lipids or fatty acids needed for plant growth. The selectivity of this herbicide is based on the difference in the speed of herbicide breakdown in the crop versus the weeds. Clodinafop-propargyl converts from the ester form to the active acid and then to biologically inactive compounds. Grass weeds such as wild oats and wild millet cannot effectively break down clodinafop-propargyl, so they are controlled as a lethal dose accumulates at the meristematic growing points. This is a post emergence, selective systemic grass herbicide and is known to control grasses such as green foxtail, barnyard grass,
Persian darnel and volunteer canary seed in wheat crops. However, it is known that clodinafop propargyl is ineffective against several broadleaved weeds.
There is a further need in the art to provide synergistic herbicide compositions as they afford various advantages. Herbicide combinations offer advantages of improved weed control, a greater spectrum of weeds controlled, reduced cost and reduced residue problems.
The present invention also provides such a synergistic herbicidal composition of clodinafop-propargyl and acifluorfen sodium.
It was further found that a major problem with clodinafop-propargyl is that it undergoes hydrolysis in the presence of an aqueous medium in acidic environment rendering it incapable of being formulated as stable formulation along with acifluorfen sodium or fomesafen sodium as a stable soluble liquid formulation.
US Patent 4285723 discloses, selective diphenyl ether herbicides including fomesafen, 5-(2-chloro-α,α,α-trifiuoro-/?-tolyloxy)-N-mesyl-2- nitrobenzenecarboximidate, and its agrochemically acceptable salts. Fomesafen sodium is a selective early post emergent herbicide used to control broad leaved weeds in soybean. US Patent No. 6369001 provides a liquid concentrate herbicidal microemulsion composition comprising water; a water-soluble herbicide and an oil-soluble cyclohexenone or aryloxyphenoxypropionate graminicide. This patent discloses many examples of water soluble herbicide such as acifluorfen and fomesafen and oil soluble cyclohexenone such as Clodinafop-propargyl. However, it does not teach the selective combinations of acifluorfen sodium or fomesafen sodium and Clodinafop propargyl. Further, this patent does not address and solve the specific degradation problem of Clodinafop- propargyl, particularly in an aqueous environment. It was found that liquid concentrates or water based formulations comprising clodinafop- propargyl and acifluorfen sodium or fomesafen sodium have poor stability and aggravate the problem of degradation of clodinafop- propargyl.
Acifluorfen sodium and fomesafen sodium are known to produce phytotoxicity to desired crop. Fomesafen sodium is formulated as Microemulsion (ME) and Soluble Liquid (SL) formulation. It is registered and marketed under the brand name of
Flexstar and Reflex and its existing foπnulations also suffer from the disadvantage of phytotoxicity.
The present inventors have also found that soluble liquid, wettable powder, water dispersible granules and also tank mixtures including acifluorfen sodium or fomesafen sodium with Clodinafop propargyl causes phytotoxicity on desired crops. Therefore, there is need in the art to provide a formulation of acifluorfen sodium or fomesafen sodium with Clodinafop propargyl that causes no phytotoxicity. Therefore, there is a long felt need in the art to provide a stable formulation comprising clodinafop propargyl and acifluorfen sodium or fomesafen sodium that solves the problems of degradation of clodinafop propargyl in aqueous medium and solves the existing problem of phytotoxicity induced by these active ingredients.
Therefore, it is desirable to provide a formulation of clodinafop- propargyl and acifluorfen sodium or fomesafen sodium that surprisingly meets the challenge of providing a storage stable formulation clodinafop- propargyl and acifluorfen sodium or fomesafen sodium which is also non phytotoxic. Hitherto, no successful attempts have been made to formulate an emulsifϊable concentrate of acifluorfen sodium or fomesafen sodium and clodinafop-propargyl. The present invention provides such a storage stable agrochemical emulsifiable concentrate of clodinafop- propargyl and acifluorfen sodium or fomesafen sodium that causes no phytotoxicity.
OBJECT OF THE INVENTION The present invention at least achieves one of the following objectives.
It is an object of the present invention to provide a herbicidal emulsifiable concentrate comprising acifluorfen sodium which does not cause phytotoxicity to desired crops.
It is a further object of the present invention to provide an emulsifiable concentrate that meets the challenge of formulating a water soluble herbicide, acifluorfen sodium in organic solvent (s). It is a further object of the present invention to provide a herbicidal emulsifiable concentrate exhibiting a broad spectrum of activity in controlling diversity of weeds and grasses present in crops.
Yet another object of the present invention is to provide a herbicidal emulsifiable concentrate comprising acifluorfen sodium and second herbicide selected from the class of aryloxyphenoxypropionates known as "fops" herbicide.
Yet another further object of the present invention is to provide a process for the preparation of a herbicidal emulsifiable concentrate comprising acifluorfen sodium.
It is also an object of the present invention to provide a synergistic herbicidal composition of clodinafop propargyl and acifluorfen sodium.
It is further object of the present invention is to provide a synergistic herbicide composition exhibiting a broad spectrum of activity in controlling diversity of broad leaf weeds and grasses present in crops.
Another object of the present invention is to provide a synergistic herbicidal composition that enhances performance of weed control thereby reducing the required application frequency of the composition to control the grassy and broadleaved weeds in a crop field.
Another object of the present invention is to provide a herbicidal composition which demonstrates a complementation of weed control activity over the application of individual herbicides separately. Yet another object of the present invention is to provide a synergistic herbicidal combination that negates the need of the sequential application of herbicides thereby reducing the environmental load of herbicides and thus are environmentally safe.
Further object of the present invention is to provide a storage stable agrochemical emulsifiable concentrate of clodinafop propargyl and acifluorfen sodium or fomesafen sodium.
It is also an object of the present invention to provide an emulsifiable concentrate that meets the challenge of formulating water soluble herbicides, acifluorfen sodium or fomesafen sodium in organic solvent.
It is further object of the present invention to solve the problem of degradation of clodinafop- propargyl in aqueous medium.
It is further object of the present invention to provide a storage stable agrochemical emulsifiable concentrate that is non-phytotoxic. Yet another object of the present invention is to provide an emulsifiable concentrate wherein the solubility profile of acifluorfen sodium or fomesafen sodium and clodinafop propargyl is improved.
Yet another object of the present invention is to provide an agrochemical composition exhibiting a broad spectrum of activity in controlling diversity of weeds and grasses present in crops. Yet another further object of the present invention is to provide process for the preparation of a storage stable agrochemical emulsifϊable concentrate of clodinafop- propargyl and acifluorfen sodium or fomesafen sodium.
SUMMARY OF THE INVENTION According to an aspect of the present invention, there is provided a non phytotoxic herbicidal emulsifϊable concentrate comprising an agrochemically effective amount of acifluorfen sodium.
According to another aspect of the present invention, there is provided a non phytotoxic herbicidal emulsifiable concentrate comprising; (i) an agrochemically effective amount of acifluorfen sodium;
(ii) at least a first organic solvent having a dielectric constant of from about 12 to about 50; and
(iii) at least a second organic solvent having a dielectric constant of from about 1 to about 4,
wherein the ratio of the said first and second organic solvents is in the range from about 4: 1 to about 0.04: 1 by weight.
According to another aspect of the present invention, there is provided a non- phytotoxic emulsifiable concentrate comprising acifluorfen sodium in an amount of about 16.5 % by weight of the composition; an organic solvent having a dielectric constant of 18.2; another organic solvent having a dielectric constant of 2.5 wherein the ratio of said organic solvents is about 1.5: 1 by weight; an emulsifying agent or mixtures thereof in an amount of about 15 % by weight of the composition; and a stabilizer in an amount of about 1 % by weight of the composition.
According to further aspect of the present invention, there is provided a non phytotoxic herbicidal emulsifiable concentrate comprising an agrochemically effective amount of acifluorfen sodium and an agrochemically effective amount of a second herbicide selected from the class of aryloxyphenoxypropionates.
According to a further aspect of the present invention, there is provided a process for the preparation of a non phytotoxic herbicidal emulsifiable concentrate comprising: (a) admixing at least one organic solvent having a dielectric constant of from about 12 to about 50 and at least another organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; and (c) adding at least one emulsifying agent in an amount of from about 0.1 % to about 40 % and at least a stabilizer in an amount of from about 0.25 to about 10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture.
According to an aspect of the present invention, there is provided a synergistic herbicidal composition comprising an agrochemically effective amount of acifluorfen sodium; and an agrochemically effective amount of clodinafop propargyl. According to another aspect of the present invention, there is provided a storage stable agrochemical emulsifiable concentrate comprising:
(i) an agrochemically effective amount of acifluorfen sodium or fomesafen sodium;
(ii) an agrochemically effective amount of clodinafop propargyl;
(iii) at least a first organic solvent having a dielectric constant of from about 12 to about 50; and
(iv) at least a second organic solvent having a dielectric constant of from about 1 to about 4,
wherein the ratio of said first and second organic solvents is in the range from about
4: 1 to about 0.04: 1 by weight.
According to another aspect of the present invention, there is provided a storage stable agrochemical emulsifiable concentrate comprising acifluorfen sodium in an amount of about 16.5 % by weight of the composition, Clodinafop propargyl in an amount of about 8 % by weight of the composition, an organic solvent having a dielectric constant of 18.2, another organic solvent having a dielectric constant of 2.5; wherein the ratio of said organic solvents is about 2:1 by weight, an emulsifying agent or mixtures thereof in an amount of about 15 % by weight of the composition, and stabilizer in an amount of about 1 % by weight of the composition. According to a further aspect of the present invention, there is provided a process for the preparation of a storage stable agrochemical emulsifϊable concentrate comprising the steps of (a) admixing at least one organic solvent having a dielectric constant of from about 12 to about 50 and at least another organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium or fomesafen sodium and an agrochemically effective amount of clodinafop propargyl to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; (c) adding at least one emulsifying agent in an amount of from about 0.1 % to about 40 % and at least a stabilizer in an amount of from about 0.25% to about
10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture and; d) filtering the resultant mixture.
DETAILED DESCRIPTION
It is thus known in the art that aqueous based formulations such as soluble liquid (SL) of acifluorfen sodium are phytotoxic. The present inventors have also found that in addition to aqueous based formulations, wettable powder and water dispersible granules of acifluorfen sodium are also phytotoxic.
Hitherto, no attempt has been made in the art to solve the problem of phytotoxicity of acifluorfen sodium formulations. The present inventors have unexpectedly and surprisingly found that an emulsifϊable concentrate formulation of acifluorfen sodium is non-phytotoxic. However, it is known in the art that there is a great difficulty in preparing an emulsifϊable concentrate when the active ingredient is a water-soluble herbicide such as acifluorfen sodium. It is believed that emulsifϊable concentrates of water soluble active ingredients such as acifluorfen sodium are difficult to formulate because of their low solubility in conventional non polar medium used for making emulsifiable concentrates. Further, emulsifiable concentrates are suitable for limited number of active ingredients only. Many active ingredients are not soluble enough to be supplied economically in this form. Hitherto, no attempts have been made in the prior art to prepare emulsifiable concentrate of acifluorfen sodium.
A person skilled in the art would expect a water soluble herbicide to dissolve in water and only partially soluble in an organic solvent. It was unexpectedly and surprisingly found that it is indeed possible to form an emulsifiable concentrate formulation comprising acifluorfen sodium in the solvent system contemplated according to the present invention. Thus, the present inventors set about providing an emulsion concentrate of acifluorfen sodium that are non- phytotoxic.
Therefore, in one aspect, the present invention provides a non- phytotoxic herbicidal emulsifiable concentrate comprising an agrochemically effective amount of acifluorfen sodium.
The term "agrochemically effective amount" is that quantity of active agent, applied in any amount which will provide the required control of broad leaved weeds and grasses. The particular amount is dependent upon many factors including, for example, the crop, weeds sought to be controlled and environmental conditions. The selection of the proper quantity of active agent to be applied, however, is within the expertise of one skilled in the art.
In an embodiment, the agrochemically effective amount of acifluorfen sodium comprises from about 0.01% to about 40% and preferably from about 0.1% to about
35% of the total weight of the compositions according to the present invention.
In a preferred embodiment, acifluorfen sodium comprises from about 15.5% to about 30 % and more preferably about 16.5% of the total weight of the compositions according to the present invention.
It was unexpectedly found by the present inventors that organic solvents having dielectric constants in predetermined ranges when used in combination in a specific weight ratio played a major role in providing emulsifiable concentrate with desired emulsifϊability, solubility profile and stability.
In an embodiment, the non-phytotoxic herbicidal emulsifiable concentrate of the present invention comprise further ingredients selected from an organic solvent having a dielectric constant from about 12 to about 50, another organic solvent having a dielectric constant from about 1 to about 4, an emulsifying agent, a stabilizer and the like.
Therefore, in yet another aspect of the present invention, there is provided a non phytotoxic herbicidal emulsifiable concentrate comprising; (i) an agrochemically effective amount of acifluorfen sodium; (ii) at least a first organic solvent having a dielectric constant of from about 12 to about 50; and (iii) at least a second organic solvent having a dielectric constant of from about 1 to about 4, wherein the ratio of the said organic solvents is in the range from about 4: 1 to about 0.04: 1 by weight.
In the following description of the present invention, the dielectric constant is denoted as ε and dielectric constant of mixture of organic solvents having dielectric constants of from about 12 to about 50 and about 1 to about 4 is denoted as εmjX.
According to the present invention, the organic solvent having a dielectric constant from about 12 to about 50 may be selected from the group comprising cyclohexanone, N-methyl pyrrolidone, dimethyl sulfoxide, acetophenone, dimethyl formamide, MIBK, butanol, isophorone, propanol, methanol, propargyl alcohol, acetone, acetonitrile, dichloromethane and the like. The said solvent may be preferably selected from cyclohexanone, N-methyl pyrrolidone, dimethyl sulfoxide, acetophenone, dimethyl formamide, MIBK, butanol according to present invention. Still more preferably, said organic solvent is cyclohexanone.
In an embodiment, the organic solvent having a dielectric constant of about 12 to about 50 comprises from about 4% to about 50% by weight of the composition, preferably from about 16 % to about 50 % by total weight of the composition according to the present invention.
According to the present invention, said another organic solvent having a dielectric constant from about 1 to about 4 may be selected from toluene, xylene, solvesso- 200, C-9, solvesso- 100, solvesso- 150 and the like. In an embodiment, the preferred the organic solvent having a dielectric constant from about 1 to about 4 is xylene.
In an embodiment, the organic solvent having a dielectric constant of from about 1 to about 4 comprises from about 4 % to about 40 % by weight of the composition, preferably from about 8 % to about 30% by total weight of the compositions according to the present invention.
In an embodiment, the organic solvents having a dielectric constants of from about 12 to about 50 and from about 1 to about 4 together comprises from about 10% to about 70% by total weight of the composition.
In an embodiment, a first organic solvent having a dielectric constant of from about
12 to about 50 and a second organic solvent having a dielectric constant of from about 1 to about 4 may be used in a predetermined specific weight ratio. Preferably, the present invention comprises utilizing said first and second organic solvents within the present emulsifiable concentrate formulations in a weight ratio of from about 4: 1 to about 0.04 : 1.
In an embodiment, the emulsifiable concentrate according to present invention provides best stability, emulsifiability and solubility when εmjX is from about 4 to about 35 and preferably when εmjX is from about 4 to about 23.
In yet another embodiment, the compositions according to the present invention comprise at least one emulsifying agent. The emulsifying agent may be preferably selected from a group comprising lignosulphonates, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, non- ionic polyethoxylates, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, calcium salts of alkyl benzene sulphonates, salts of sulfonated naphthalene, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids and salts of phenol sulfonic acids.
More preferably, the emulsifying agent may be selected from a group comprising ethoxylated alkyl phenols, alkyl benzene sulfonates and calcium salts of alkyl benzene sulfonates.
In another embodiment, the preferred emulsifying agent may also be selected from the group comprising nonyl phenol ethoxylate, styrenated phenol ethoxylate, castor oil ethoxylate, calcium dodecyl benzene sulphonate, sodium tetrapropylene benzenesulfonate, sodium 6- dodecylbenzenesulfonate and mixtures thereof.
The emulsifying agent is preferably used in an amount of about 0.1 to about 40.0 %,' and preferably from about 1.0 to about 30.0 % by total weight of the compositions according to the present invention. In another preferred embodiment, the emulsifying agent is present in an amount of about 2.0 to about 20.0 % by total weight of the compositions. In an embodiment, the compositions according to present invention additionally comprises stabilizer.
The stabilizer may be preferably selected from butanol, propanol, propargyl alcohol, acetic anhydride, acetic acid, epichlorohydrin and epoxidised soybean oil and like. The stabilizer is preferably used in an amount of about 0.25% to about
10%.
The storage stability of the present emulsion concentrate is dependent, inter alia, on the pH of the final formulation.
In an embodiment, the emulsifiable concentiate of the present invention affords excellent storage stability in a pH range of from about 4.0 to about 6.0.
According to a further aspect of the present invention, the non phytotoxic herbicidal emulsifiable concentrate according to the present invention are prepared by a process comprising: (a) admixing at least a first organic solvent having a dielectric constant of from about 12 to about 50 and at least a second organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; and (c) adding at least one emulsifying agent in an amount of from about 0.1% to about 40% and additionally adding a stabilizer in an amount of from about 0.25 to about 10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture. In an embodiment, said process for the preparation of a non-phytotoxic herbicidal emulsifiable concentrate additionally comprises filtering the resultant mixture obtained in step (c) of the previous aspect of the present invention.
In an embodiment, the non-phytotoxic herbicidal emulsifiable concentrate comprising acifluorfen sodium further comprises a second herbicide selected from class of aryloxyphenoxypropionates, called as "fops".
Therefore, in another aspect, the present invention provides a non- phytotoxic herbicidal emulsifiable concentrate comprising an agrochemically effective amount of acifluorfen sodium and a second herbicide selected from the class of aryloxyphenoxypropionates known as "fops" herbicide.
According to present invention, the "fops" herbicide comprises a herbicide selected from the group comprising clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, fluazifop-butyl, fluazifop-P-butyl, haloxyfop, propaquizafop, quizalofop and quizalofop-P.
In an embodiment, "fops" herbicide comprises' from about 0.1% to about 50%, preferably from about 1.0% to about 40% by total weight of the compositions according to the present invention. More preferably, said second herbicide comprises about 8% by total weight of the composition according to the present invention. In an embodiment, the non-phytotoxic herbicidal emulsifiable concentrate comprising an agrochemically effective amount of acifluorfen sodium and a second herbicide is prepared by the procedure described hereinabove.
The present inventors have also unexpectedly and surprisingly found that selective combination of acifluorfen sodium and clodinafop propargyl is synergistic and has broad spectrum of activity. A person skilled in the art would not expect that selecting acifluorfen sodium from known diphenyl ether herbicides, known as "fen" herbicides and Clodinafop propargyl from aryloxyphenoxypropionates, known as
"fop" herbicides and combining the same would provide synergistic herbicidal activity. Λ
There is a constant need in the art for herbicidal compositions that are synergistic. Herbicide combinations offer advantages of improved weed control, a greater spectrum of weeds controlled, reduced cost and reduced residue problems. However, the underlying mechanism by which a combination of herbicides results in synergistic action is unknown to a person skilled in the art.
Thus, the present inventors set about providing a herbicidal composition that is synergistic.
Therefore, in one aspect, the present invention provides a synergistic herbicidal composition comprising an agrochemically effective amount of acifluorfen sod.ium; and an agrochemically effective amount of clodinafop propargyl. In an embodiment, clodinafop propargyl comprises from about 0.1% to about 50%, preferably from about 1.0% to about 40%, more preferably 2-10% by total weight of the compositions according to the present invention. Most preferably, clodinafop propargyl comprises about 8% by total weight of the composition according to the present invention.
According to present invention, the synergistic herbicidal compositions can be either solid or liquid formulations or solutions. For example, the herbicidal compositions of the present invention can be formulated as soluble liquid, water based emulsions, suspension concentrates, wettable powders, emulsifiable concentrates, dusts, water dispersible granules, aerosols, or flowable emulsion concentrates. In such formulations, the compounds are extended with a liquid or solid carrier and, when desired, suitable surfactants are incorporated. In a most embodiment of this aspect of the invention described hereinafter, the synergistic compositions according to the present invention may be formulated as emulsifiable concentrates.
The synergistic herbicidal compositions of the present invention may include adjuvants, such as wetting agents, spreading agents, dispersing agents, stickers, adhesives, and the like, in accordance with agricultural practices and the formulation type. The selection of the adjuvants according to the desired formulation type is within expertise of the person skilled in the art and is not particularly limiting. The synergistic herbicidal compositions of the present invention can be prepared according the conventional procedure used for formulating desired formulation type and is within the expertise of the person skilled in the art.
In other embodiments, the formulations comprising the synergistic combination of acifluorfen sodium and clodinafop propargyl may be formulated using the ingredients and the process for the preparation of non phytotoxic emulsifiable concentrate comprising acifluorfen sodium.
In an embodiment, the compositions according to the present invention optionally comprise a safener. Preferably, the safener is cloquintocet-mexyl that accelerates the rate of clodinafop-propargyl break down in crops, thus preventing the accumulation of a lethal dose.
In a preferred embodiment, the safener is present in an amount of about 0.1% to about 30% by weight of the second active ingredient component, preferably 1% to about 15% by weight of clodinafop acid or an agrochemically acceptable salt or an ester thereof.
The present inventors have further found that soluble liquid or water based formulation comprising clodinafop propargyl and acifluorfen sodium or fomesafen sodium had poor stability. The inventors conducted experiments on the soluble liquid formulations comprising these two active ingredients and observed that a soluble liquid composition comprising acifluorfen sodium or fomesafen sodium and clodinafop propargyl was highly unstable and quickly degraded rendering the composition incapable of being used. In order to solve the problem of water mediated degradation of clodinafop propargyl, it was essential to co-formulate clodinafop propargyl and acifluorfen sodium or fomesafen sodium wherein the use of aqueous phase is completely eliminated thereby solving the instability problem of clodinafop propargyl. An emulsifϊable concentrate is the example of such formulation type. However, there is a great difficulty of preparing an emulsifϊable concentrate when active ingredient is a water-soluble herbicide such as acifluorfen sodium or fomesafen sodium. It was known that emulsifϊable concentrates of water soluble active ingredients such as acifluorfen sodium or fomesafen sodium were difficult to formulate because of their low solubility in conventional non polar medium used for making emulsifϊable concentrates. It is known in the art that emulsifϊable concentrates are suitable for limited number of active ingredients only. Many active ingredients are not soluble enough to be supplied economically in this form.
A person skilled in the art would expect a water soluble herbicide salt to dissolve in water and only partly soluble in an organic solvent. It was unexpectedly and surprisingly found that it is indeed possible to form an emulsifϊable concentrate formulation comprising a water-soluble herbicide using a combination of organic solvents having predetermined dielectric constants. The present inventors have surprisingly found that the dielectric constant of organic solvents play a major role in imparting storage stability, emulsifϊability and solubility profile to the emulsifϊable concentrate of acifluorfen sodium or fomesafen sodium and clodinafop propargyl. It was unexpectedly found that organic solvents having dielectric constants in predetermined ranges when used in combination in a specific weight ratio played a major role in providing desired emulsifiable concentrate. The present inventors have formulated the emulsifiable concentrate including clodinafop propargyl and acifluorfen sodium or fomesafen sodium based on these surprising findings that provides excellent storage stability, emulsifiablity and solubility profile to the final formulation.
The present inventors have also found that aqueous formulation, wettable powder, water dispersible granules and the tank mixtures of acifluorfen sodium or fomesafen sodium and Clodinafop propargyl cause phytotoxicity to the desired crops.
It was surprisingly found by the present inventors that emulsifiable concentrate formulation of acifluorfen sodium or fomesafen sodium with clodinafop propargyl solved the problem of phytotoxicity to the desired crops. Thus, the present inventors set about providing a composition that is storage stable and non- phytotoxic.
Therefore, in one aspect, the present invention provides a storage stable agrochemical emulsifiable concentrate comprising;
(i) an agrochemically effective amount of acifluorfen sodium or fomesafen sodium;
(ii) an agrochemically effective amount of clodinafop propargyl;
(iii) at least a first organic solvent having a dielectric constant of from about 12 to about 50; and (iv) at least a second organic solvent having a dielectric constant of from about 1 to about 4,
wherein the ratio of the said organic solvents is in the range from about 4: 1 to about 0.04: 1 by weight.
When the preferred water soluble herbicide is fomesafen sodium, it is present in an amount of from about 4 % to about 8 % and preferably about 8.4 % of the total weight of the compositions according to the present invention.
In this embodiment of the present invention, the amount of clodinafop propargyl, the selection of preferred organic solvents and their respective percentages to achieve desirable properties of the end- formulation, the selection and amount of preferred emulsifying agents, the choice of suitable stabilizers, the preferred pH range, the selection of preferred safeners etc. are as per the preceding aspects and embodiments of the present invention, which are reproduced herein in its entirety.
In an embodiment, the emulsifiable concentrate according to present invention provides best stability, emulsifiability and solubility when εn,iX is from about 4 to about 35 and preferably when εnijX is from about 4 to about 23. However, it should be understood that εmjXof the selected ratio of solvents is not particularly limiting as long as the desired ratio of the solvents is maintained.
In a preferred embodiment, the emulsifiable concentrate formulations according to the present invention are prepared by a process comprising (a) admixing at least a first organic solvent having a dielectric constant of from about 12 to about 50 and at least a second organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium or fomesafen sodium and an agrochemically effective amount of clodinafop propargyl to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; (c) adding at least one emulsifying agent in an amount of from about 0.1% to about 40% and at least one stabilizer in an amount of from about 0.25% to about 10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture and; d) filtering the resultant mixture.
The formulations as described above have selective herbicidal action for crop plants and weeds. Such a selective herbicidal action renders the composition useful to control the following weeds.
Monocotyledon weeds or grassy weeds of the genera such as wild oats (Avena), crabgrass {Digitaria), barnyardgrass (Echinochloa), goosegrass (Eluesin), millet grass {Panicum), foxtail (Setaria.), bermudagrass (Cynodon), Blue grass (Poa), sorghum (sorghum), bulrush (Scripus), quackgrass (Agropyron) and arrow grass
(sagittaήa)
Dicotyledon weeds or broad leaved weeds of the genera such as lambsquarters (Chenopodium), pigweeds (Amaranthus), purslane (Portulaca), morning glory (Ipomoea), nightshade (Solanum), spurge (Euphorbia), ragweed (Ambroasia), small melon (Cucumis), starbur (Acanthospermum), cocklebur (Xanthium),ground cherry (Physalis), annual nettle (Urtica), knotweed (Polygonum), speedwell (Veronica), thomapple (Datura), acalypha {Acalypha), Leucas, wild jute (Corchorus), Digera, Parthenium, Commelina, Celosia, Phyllanthus, Chrozophora, Ocimum, Grangia, Capsella, Vicia, Celoma, and Cyperus haspan.
The formulations of the present invention have a selective herbicidal action and may be used for post emergence weed control in various crops viz. Soybean, Green gram, Black gram, Groundnut, wheat and pea. Further, this composition may also be used as inter row directed application as post emergence weed control and pre planting application in case of zero tillage cultivation before planting of crop in some susceptible crops such as cotton, potato, tomato, chilli, sugarcane, onion, cucurbits, cabbage, cauliflower, beets (especially sugarbeets), sunflowers, rapeseeds and for achieving an effective weed control in perennial crops (grape vines and orchards).
The formulations of the present invention can be used as post emergence application to control wide range of weeds from weeds stage of 1 -2 leaf stage to 4 to 6 tilling/ branching stage, preferably 2 to 4 leaf stage or 7 to 60 days after sowing of crop, preferably 15 to 25 days after sowing of crop.
The following examples illustrate the present invention. The exemplified formulations were prepared using processes that are described above for the preparation of such formulations. The Examples described herein does not limit the scope of the invention as described herein above. Experimental Examples- 1
Example 1; Acifluorfen sodium 16.5 % w/w EC were prepared as follows:
Figure imgf000030_0001
Cyclohexanone and xylene were mixed in required quantity in a mixing vessel to form a first homogeneous mixture. Then required quantity of acifluorfen sodium was added at ambient temperature and stirred to form a second homogenous mixture. Calcium dodecyl benzene sulfonate and nonyl phenol ethoxylate and stabilizer were added to the second homogenous mixture with stirring to obtain a homogenous mixture, which was filtered to obtain the target emulsifiable concentrate.
Example 2
Figure imgf000030_0002
Acifluorfen sodium 16.5 % w/w including combination of N-methyl pyrrolidone and xylene was prepared as per the procedure of Example 1.
Experimental Examples- 2 Example 1
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC was prepared as follows:
Figure imgf000031_0001
Cyclohexanone and xylene were mixed in required quantity in a mixing vessel to form a first homogeneous mixture. Then required quantity of acifluorfen sodium and clodinafop propargyl wasadded at ambient temperature and stirred to form a second homogenous mixture. Calcium dodecyl benzene sulfonate and nonyl phenol ethoxylate and stabilizer were added to the second homogenous mixture with stirring to obtain a homogenous mixture and then filtered the resultant mixture.
Example 2
Figure imgf000032_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of N-methyl pyrrolidone and xylene in a weight ratio of 4: 1 was prepared as per the process of Example 1.
Experimental Examples- 3
Example 1
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC λvas prepared as follows:
Figure imgf000032_0002
Cyclohexanone and xylene were mixed in required quantity in a mixing vessel to form a first homogeneous mixture. Then required quantity of acifluorfen sodium and clodinafop propargyl wereadded at ambient temperature and stirred to form a second homogenous mixture. Calcium dodecyl benzene sulfonate and nonyl phenol ethoxylate and stabilizer wereadded to the second homogenous mixture with stirring to obtain a homogenous mixture and then filtered the resultant mixture.
Example 2
Figure imgf000033_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of N-methyl pyrrolidone and xylene in a weight ratio of 2.05:1 was prepared as per the process of Example 1.
Example 3
Figure imgf000033_0002
Figure imgf000034_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of Acetophenone and xylene in a weight ratio of 3.48:1 was prepared as per the process of Example 1.
Example 4
Figure imgf000034_0002
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 0.579:1 was prepared as per the process of Example 1.
Example 5
Figure imgf000034_0003
Figure imgf000035_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of Dimethyl formamide and toluene in a weight ratio of 0.17: 1 was prepared as per the process of Example 1.
Example 6
Figure imgf000035_0002
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of dimethyl sulfoxide and xylene in a weight ratio of 0.20:1 was prepared as per the process of Example 1.
Example 7
Figure imgf000035_0003
Figure imgf000036_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of N-methyl pyrrolidone and xylene in a weight ratio of 0.92:1 was prepared as per the process of Example 1.
Example 8
Figure imgf000036_0002
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of dimethyl formamide and xylene in a weight ratio of 0.043:1 was prepared as per the process of Example 1.
Example 9
Figure imgf000036_0003
Figure imgf000037_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 2.24:1 was prepared as per the process of Example 1.
Example 10
Figure imgf000037_0002
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 2.14:1 was prepared as per the process of Example 1.
Example 11
Figure imgf000037_0003
Figure imgf000038_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 1.99:1 was prepared as per the process of Example 1.
Example 12
Figure imgf000038_0002
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 1.99:1 was prepared as per the process of Example 1.
Example 13
Figure imgf000038_0003
Figure imgf000039_0001
Fomesafen sodium 8.4 % w/w and Clodinafop- propargyl 4.25 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 3.75:1 was prepared as per the process of Example 1.
Example 14
Figure imgf000039_0002
Fomesafen sodium 5.6 % w/w and Clodinafop- propargyl 2.8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 3.89:1 was prepared as per the process of Example 1.
Example 15
Figure imgf000039_0003
Figure imgf000040_0001
Fomesafen sodium 4.2 % w/w and Clodinafop- propargyl 2.12 % w/w EC including combination of cyclohexanone and toluene in a weight ratio of 3.68:1 was prepared as per the process of Example 1.
Example 16
Figure imgf000040_0002
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 1.74:1 was prepared as per the process of Example 1.
Example 17
Figure imgf000040_0003
Figure imgf000041_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 1.65:1 was prepared as per the process of Example 1.
Example 18
Figure imgf000041_0002
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 1.80:1 was prepared as per the process of Example 1.
Example 19
Figure imgf000041_0003
Figure imgf000042_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of cyclohexanone and xylene in a weight ratio of 1.75: 1 was prepared as per the process of Example 1.
Example 20
Figure imgf000042_0002
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of dimethyl sulfoxide and xylene in a weight ratio of around 5:1 was prepared as per the process of Example 1.
Example 21
Figure imgf000042_0003
Figure imgf000043_0001
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of dimethyl formamide and xylene in a weight ratio of 0.025:1 was prepared as per the process of Example 1.
Example 22
Figure imgf000043_0002
Acifluorfen sodium 16.5 % w/w and Clodinafop- propargyl 8 % w/w EC including combination of N-methyl pyrrolidone and xylene in a weight ratio of 0.034: 1 was prepared as per the process of Example 1.
The emulsifiable concentrates prepared as per the Examples 1 to 22 including combination of different organic solvents having dielectric constant between the specified ranges as discussed above and varied weight ratios were tested for storage stability, solubility and emulsifiability. It was observed that formulations prepared according to Examples 1-19 were stable and showed excellent solubility and emulsifiability whereas the formulations prepared as per the Examples 20-22 showed separation of emulsifiable concentrate on storage and therefore had poor stability.
CHECK 16-19
The following experimental studies were conducted by using combination of organic solvents for conducting studies of storage stability, solubility and emulsifiability.
Experiments conducted by using combination of organic solvents in varied Λveight ratio
The emulsifiable concentrates prepared for the purpose of experiment includes
10 combination of organic solvents having a dielectric constant in a range from about 12 to about 50 and from about 1 to 4 in different weight ratios. The parameters like storage stability, solubility and emulsifiability were tested. The results of the experiments are included in following table:
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Conclusion :
The results of the above table show that the combination of organic solvent 1 having a dielectric constant of from about 12 to 50 and organic solvent 2 having a dielectric constant of from about 1 to 4 provide excellent storage stability, solubility and emulsifiability in a ratio of 0.04: 1 to 4: 1. It is clearly evident from the table that storage stability, solubility and emulsifiability of the emulsifϊable concentrate are not simultaneously achievable when the organic solvent 1 and organic solvent 2 are not present within the predetermined ratio.
10 Phytotoxicity Evaluation: Field trials for Phototoxicity
(a) EC formulation of Acifluorfen sodium
1. Comparison of phytotoxicity on soybean
Details of experiment: a) Test layout Randomized Block design
15 b) Replication Three c) Treatments Thirteen d) Plot size 24.5 sq. m e) Spacing 40 cm x 15 cm f) Test Crop Soybean g) Variety : JS 335 h) Time of application: 20 days after sowing i) Application volume : 500 liters water per hactare j) Observations days : 3, 7 and 21 days after application k) Treatment details :
Figure imgf000049_0001
* Formulation on w/w basis
Experimental Methods:
Seeds of soybeans (Glycine max) were planted in the field to conduct a trial to assess phytotoxicity effect of different formulations of Acifluorfen sodium viz. WP, WDG, SL and EC. The trial was laid out in Randomized Black Design (RBD) with thirteen treatments including untreated control, replicated three times. For each treatments plot size of 24.5 sq.m was maintained. To raise the crops, all the agronomical practices were followed as usually adopted for soybean cultivation. The test herbicidal compound, acifluorfen sodium with prescribed doses was applied using hand operated knapsack sprayer fitted plat fan nozzle. The spray volume was used at 500 //ha for application of all treatments. Untreated control plot was also sprayed by 500 / /ha water without adding any herbicides. Observation on phytotoxicity viz leaf scorching, was recorded at 3, 7 and 21 days after application of treatments from ten plants which were randomly selected from each plot. Three
10 leaves from each selected plant were scored using 0 - 10 rating scale; whereas 0= No phytotoxicity; 1=1-10% leaf scorching; 2=11-20% leaf scorching; 3=21- 30% leaf scorching; 4=31-40% leaf scorching; 5=41-50% leaf scorching; 6=51- 60% leaf scorching; 7=61-70% leaf scorching; 8=71-80% leaf scorching; 9=81- 90% leaf scorching; 10= 91-100% leaf scorching.
15
Percent phytotoxicity was determined using the following formula.
Sum of all scores % Phytotoxicity = X 100
Number of samples x Highest rating scale
20
Table 1 Phytotoxic effect (leaf scorching) on soybean crop influenced by different herbicidal treatment
Figure imgf000050_0001
Figure imgf000051_0001
* Means of three replications
Results
In the field trials, phytotoxicity of Acifluorfen sodium WP, Acifluorfen sodium WDG and Acifluorfen sodium (Blazer) SL on soybean were compared with formulations according to the present invention (EC formulation of Acifluorfen sodium) . The results of the field trial presented in table 1 indicated that Aciflourfen sodium SL (Blazer), Acifluorfen sodium WP and Acifluorfen sodium WDG caused significant crop phytotoxicity, i.e. leaf scorching while Acifluorfen sodium EC formulations were safe and did not cause phytotoxicity on the crop. 2, Comparison of phytotoxicity on Black gram Details of experiment: a) Crop : Black gram b) Variety : T-9 c) Trial Design : Randomizeb Block Design d) Replications : three e) Treatment thirteen f) Plot size 24.5 sq.m g) Spacing 40cm x 15 cm h) Time of application 20 days after sowing (DAS) i) Water volume 500 //ha j) spray equipment Hand operated knapsack sprayer k) Nozzle type Plat fan (62')
1) Observations : 3, 7, and 21 days after treatment
Experimental Methods:
Seeds of black gram were planted in the field to conduct a trial to assess phytotoxicity effect of different formultions of Acifluorfen sodium viz. WP, WDG, SL and EC. The trial was laid out in Randomized Black Design (RBD) with thirteen treatments including untreated control, replicated three times. For each treatments plot size of 24.5 sq.m was maintained. To raise the crops, all the agronomical practices was followed as usually addopted for soybean cultivation. The test herbicidal compound, Acifluorfen sodium with prescribed doses was applied using hand operated knapsack sprayer fitted plat fan nozzle. The spray volume was used at 500 //ha for application of all treatments. Untreated control plot was also sprayed by 500 / /ha water without adding any herbicides. Observation on phytotoxicity (leaf scorching) was recorded at 3, 7 and 21 days after application of treatments from ten plants which were randomly selected from each plots. Three leaves from each selected plant were rated using 0 to 10 rating scale.
Table 2 Phytotoxic effect (leaf scorching) on black gram crop influenced by different herbicidal treatment
Figure imgf000053_0001
*Mean of three replications Results
In the field trials, phytotoxicity of Acifluorfen sodium WP, Acifluorfen sodium WDG and Acifluorfen sodium (Blazer) SL on black gram were compared with formulations of present invention (EC foπnulation of acifluorfen sodium). The results of the field trial showed that Acifluorfen sodium SL (Blazer), Acifluorfen sodium WP, and Acifluorfen sodium WDG resulted into crop phytotoxicity, i.e. leaf scorching while Acifluorfen sodium EC formulations were safe and there was no phytotoxicity on crop.
Bio-efficacy Evaluation of synergistic composition of acifluorfen sodium and clodinafop propargyl.
Field trials were conducted using the combination of acifluorfen sodium and Clodinafop- propargyl according to the present invention. The emulsifiable concentrate of acifluorfen sodium and Clodinafop propargyl was used for the purpose of field trials. However, the other formulations types for e.g. soluble liquid, water based emulsions, suspension concentrates, wettable powders, dusts, water dispersible granules, aerosols, or flowable emulsion concentrates and the like are within the scope of the present invention and the below studies exemplified with a emulsifiable concentrate formulation are not intended to limit the scope of the present invention.
This experiment shows the significantly superior bioefficacy of the combination of
Acifluorfen sodium and Clodinafop propargyl against grasses and broad leaf weeds as post emergent selective herbicides in soybean and black gram. Combination of two active ingredients was prepared by mixing sodium acifluorfen with clodinafop propargyl, which are individually known for broad leaf weeds killer and grassy weeds killer, respectively, in an amount to obtain about a 16.5% (w/v) sodium acifluorfen and 8% (w/v) clodinafop propargyl, respectively in an emulsifiable concentrated (EC) formulation.
The bioefficacy was observed by counting the weed density from test field treated with test herbicidal compounds, acifluorfen sodium (EC) and Clodinafop propargyl
(EC) individually and ready mix combination of acifluorfen sodium and clodinafop propargyl formulated in emulsifiable concentrate. The crops considered was soybeans (Glycine max) and black gram (Phaseolus mungo Roxb) for test.
Experimental Methods:
Seeds of soybeans (Glycine max) and black gram (Phaseolus mungo Roxb) were planted in field to conduct a filed trial to assess the bioefficacy of Acifluorfen sodium and Clodinafop propargyl alone and combination of Acifluorfen sodium and Clodinafop propargyl. The trial was laid out in Randomized Black Design
(RBD) with thirteen treatments including untreated control, replicated three times. For each treatments plot size of 35 sq.m was maintained. To raise the crops all the agronomical practices were followed as usually adopted. The test herbicidal compounds, Acifluorfen sodium and Clodinafop propargyl alone and combination of Acifluorfen sodium and Clodinafop propargyl formulated in emulsifiable concentrate formulation with prescribed dose, were applied using hand operated knapsack sprayer fitted plat fan nozzle. The spray volume was used at 500 //ha for application of all herbicidal compounds. Untreated control plot was also sprayed by 500 / /ha water without adding any herbicides. Observations on bioefficacy was taken by taking dry weight of weeds, grassy and broad leaf weeds separately, at 30 days after treatment and per cent weed control was calculated by using following formula (Anderson 1963):
Weed dry weight in treatment Per cent weed control = (1- - — ) x 100
Weed dry weight in untreated Synergism of combination was calculated by Colby's formula
E= X + Y- ((X * Y)/100)
Whereas
E= Expected % control by mixture of two products A and B in a defined dose.
X= Observed % control by product A
Y= Observed % control by product B
Test 1: Bio-efficacy in Soybean Details of experiment a) Crop : Soybean (var: JS 335) b) Target weeds : Grassy and broad leaf weeds c) Experiment season : Kharif 2008 d) Trial Design :' Randomizeb Block Design e) Replications : three f) Treatment : thirteen g) Plot size : 7m x 5m = 35 sq.m h) Application time : 20 days after sowing (DAS) i) Water volume : 500 //ha j) spray equipment : Hand operated knapsack sprayer attached Flat fan nozzle. Table 1 Synergistic effect of combination of Acifluorfen sodium + Clodinafop propargyl against grassy and broad leaf weeds in soybean
Figure imgf000057_0001
Figure imgf000058_0001
* Mean of three replications,; GW= Grassy weeds, BLW=Broad lead weeds
Conclusion:
The above table clearly shows that there is a significant difference in the percentage weed control of (i) acifluorfen sodium alone and clodinafop propargyl alone; and (ii) combination of acifluorfen sodium and clodinafop propargyl. Acifluorfen sodium alone, found effective against broad leaf weeds and to some extent grassy weeds also, whereas clodinafop propargyl alone, found effective against grassy weeds only. However, when acifluorfen sodium and Clodinafop propargyl are combined, it is observed that combination of acifluorfen sodium and clodinafop propargyl exhibit and show greater efficiency and efficacy in controlling grassy as well as broad leaf weeds as compared to individual application. Such result is not achieved with the individual application of two actives.
It is evident from the results of the above table particularly from Sr. No 9 to 12 that there is a marked increase in the percentage of weed control, against grassy as well as broad leaves weeds when acifluorfen sodium and clodinafop propargyl are used in combination. The results conclude that there is a significant difference in the expected and actual weed control with the combination of acifluorfen sodium and clodinafop propargyl, thus indicative of synergistic activity as per Colby's formula.
Test 2: Bio-efficacy in Black Gram Details of experiment a) Crop : Black gram b) Variety : T-9 c) Experiment season : Rabi 2007-08 d) Trial Design : Randomizeb Block Design e) Replications : three f) Treatment thirteen g) Plot size 7m x 5m = 35 sq.m h) Spacing 40cm x 15 cm i) Application time 25 days after sowing (DAS) j) Water volume 500 //ha k) spray equipment Hand operated knapsack sprayer
1) Nozzle type : Plat fan Table 2 Synergistic effect of combination of Acifluorfen sodium + Clodinafop propargyl against grassy and broad leaf weeds in Black gram
Figure imgf000060_0001
Figure imgf000061_0001
* Mean of three replications; GW= Grassy weeds, BLW=Broad leaved weeds
Conclusion:
The above table clearly shows that there is a significant difference in the percentage weed control of (i) acifluorfen sodium alone and clodinafop propargyl alone; and (ii) combination of acifluorfen sodium and clodinafop propargyl. Acifluorfen sodium alone, found effective against broad leaf weeds and to some extent grassy 0 weeds also, whereas clodinafop propargyl alone, found effective against grassy weeds only. However, when acifluorfen sodium and Clodinafop propargyl are combined, it is observed that combination of acifluorfen sodium and clodinafop propargyl exhibit and show greater efficiency and efficacy in controlling grassy as well as broad leaf weeds as compared to individual application. Such result is not 5 achieved with the individual application of two actives.
It is evident from the results of the above table particularly from Sr. No 9 to 12 that there is a marked increase in the percentage of weed control, against grassy as well as broad leaves weeds when acifluorfen sodium and clodinafop propargyl are used in combination. The results conclude that there is a significant difference in the expected and actual weed control with the combination of acifluorfen sodium and clodinafop propargyl, thus indicative of synergistic activity as per Colby's formula.
Studies of phytotoxicity for storage stable formulation of Clodanafop- propargyl and acifluorfen sodium
Tank mixture of acifluorfen sodium and clodinafop propargyl and ready mix of the acifluorfen sodium and Clodinafop propargyl in different formulation types was prepared as Example 1, Example 2, Example 3 and Example 4 as follows
Example 1:
Figure imgf000062_0001
Figure imgf000063_0001
Example 2:
Figure imgf000063_0002
Example 3:
Figure imgf000064_0001
Example 4:
Figure imgf000064_0002
Figure imgf000065_0001
Comparison of Phy to toxicity:
The crops considered for phytotoxicity evaluation was Soybean (Glycine max) and Black gram (Phaseolus mungo) Roxb) for test.
Experimental Methods:
Tank mixture of acifluorfen sodium and Clodinafop propargyl and ready mix of the acifluorfen sodium and Clodinafop propargyl in different formulation types was prepared as Example 1, Example 2, Example 3 and Example 4 and phytotoxicity on test were compared through field trials. The trial was laid out in Randomized Black Design (RBD) with nine treatments including untreated control, replicated three times for each example. For each treatments plot size of 24.5 sq.m was maintained. To raise the crops, all the agronomical practice was followed as usually adopted for soybean and black gram cultivation. The test herbicidal compounds, with prescribed doses were applied using hand operated knapsack sprayer fitted plat fan nozzle. The spray volume was used at 500 //ha for application of all treatments. Untreated control plot was also sprayed by 500 / /ha water without adding any herbicides. Observation on phytotoxicity (leaf scorching) was recorded at 3, 7 and 21 days after application of treatments from ten plants which were randomly selected from each plot. Test -1: Comparison of phytotoxicity on soybean.
Details of experiment: a) Test layout Randomized Block design b) Replication Three c) Treatments Nine d) Plot size 24.5 sq. m e) Spacing 40 cm x 15 cm f) Test Crop Soybean g) Variety JS 335 h) Time of application: 20 days after sowing i) Application volume : 500 liters water per hactare j) Observations days : 3, 7 and 21 days after application
Table 1 Phytotoxic effect (leaf scorching) on soybean crop influenced by different herbicidal treatment (Example 1)
Figure imgf000066_0001
Figure imgf000067_0001
*Mean of three replications
Table 2 Phytotoxic effect (leaf scorching) on soybean crop influenced by different herbicidal treatment (Example2)
Figure imgf000067_0002
Figure imgf000068_0001
*Mean of three replications
Table 3 Phytotoxic effect (leaf scorching) on soybean crop influenced by different herbicidal treatment (Example 3)
Figure imgf000068_0002
Figure imgf000069_0001
*Mean of three replications
Table 4 Phytotoxic effect (leaf scorching) on soybean crop influenced by different herbicidal treatment (Example 4)
Figure imgf000069_0002
*Mean of three replications
Test -2: Comparison of phytotoxicity on black gram.
Details of experiment: a) Crop : Black gram (var. T-9) b) Trial Design : Randomizeb Block Design c) Treatments : Thirteen, replicated thrice d) Plot size 24.5 sq.m e) Spacing 40cm x 15 cm f) Time of application 20 days after sowing (DAS) g) Water volume 500 //ha h) spray equipment Hand operated knapsack sprayer i) Nozzle type Plat fan
Table 5 Phytotoxic effect (leaf scorching) on Black gram crop influenced by different herbicidal treatment (Example 1)
Figure imgf000070_0001
Figure imgf000071_0001
*Mean of three replications
Table 6 Phytotoxic effect (leaf scorching) on Black gram crop influenced by different herbicidal treatment (Example2)
Figure imgf000071_0002
*Mean of three replications Table 7 Phytotoxic effect (leaf scorching) on Black gram crop influenced by different herbicidal treatment (Example 3)
Figure imgf000072_0001
*Mean of three replications Table 8 Phytotoxic effect (leaf scorching) on Black gram crop influenced by different herbicidal treatment (Example4)
Figure imgf000073_0001
*Mean of three replications
Results
The results of the field trial, presented in table 1 to 8, show that tank mix combinations as well as ready mix combination of Example 1, Example 2 and Example 3 resulted into phytotoxicity (leaf scorching) on Soybean and Black gram crop, which was found to have slightly recovered after 7 days. Example 4 EC formulation according to the present inventionwas found to be safe for Soybean and Black gram crop and there was no adverse effect on crop.

Claims

1. A non phytotoxic herbicidal emulsifiable concentrate comprising an agrochemically effective amount of acifluorfen sodium.
2. A process for the preparation of non phytotoxic herbicidal emulsifiableconcentrate comprising: (a) admixing at least a first organic solvent having a dielectric constant of from about 12 to about 50 and at least a second organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; and (c) adding at least one emulsifying agent in an amount of from about 0.1% to about 40% and optionally adding a stabilizer in an amount of from about 0.25 to about 10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture.
3. A non phytotoxic herbicidal emulsifiable concentrate comprising;
(i) an agrochemically effective amount of acifluorfen sodium or fomesafen sodium;
(ii) at least a first organic solvent having a dielectric constant of from about 12 to about 50;
(iii) at least a second organic solvent having a dielectric constant of from about 1 to about 4; and (iv) optionally comprising at least one ingredient selected from an emulsifying agent and a stabilizer;
wherein the ratio of the said first and second organic solvents is in the range from about 4: 1 to about 0.04: 1 by weight.
4. A non-phytotoxic emulsifϊable concentrate comprising acifluorfen sodium in an amount of about 16.5 % by weight of the composition; a first organic solvent having a dielectric constant of 18.2; a second organic solvent having a dielectric constant of 2.5 wherein the ratio of said first and second organic solvents is about 1.5: 1 by weight; an emulsifying agent or mixtures thereof in an amount of about 15 % by weight of the composition; and a stabilizer in an amount of about 1 % by weight of the composition.
5. A synergistic herbicidal composition comprising an agrochemically effective amount of acifluorfen sodium; and an agrochemically effective amount of clodinafop propargyl.
6. The synergistic herbicidal composition as claimed in claim 1 or claims 3-5 wherein said acifluorfen sodium comprises from about 0.01% to about 40% and preferably from about 15.5% to about 30 % and more preferably about 16.5% of the total weight of the compositions.
7. The synergistic herbicidal composition as claimed in claim 6 wherein the said Clodinafop propargyl comprises from about 0.1% to about 50%, preferably from about 1.0% to about 40% and more preferably about 8% by total weight of the compositions.
8. The synergistic herbicidal composition as claimed in claim 1 or claims 3- 7, wherein said composition is formulated as soluble liquid, water based emulsions, suspension concentrates, wettable powders, emulsifiable concentrates, dusts, water dispersible granules, aerosols, or flowable emulsion concentrates.
9. The synergistic herbicidal compositions of claim 1 or claims 3-8 additionally comprising at least one ingredient selected from wetting agents, spreading agents, dispersing agents, stickers and adhesives.
10. The synergistic herbicidal composition as claimed in claims 3-9 wherein said fomasafen sodium comprises from about 4 % to about 8 %, more preferably about 8.4 % of the total weight of the compositions.
11. The emulsifiable concentrates as claimed in claims 3-10 wherein said first organic solvent having a dielectric constant from about 12 to about 50 is selected from the group comprising cyclohexanone, N-methyl pyrrolidone, dimethyl sulfoxide, acetophenone, dimethyl formamide, MIBK, butanol, isophorone, propanol, methanol, propargyl alcohol, acetone, acetonitrile and dichloromethane.
12. The emulsifiable concentrates as claimed in claim 11, wherein said first organic solvent is cyclohexanone.
13. The emulsifϊable concentrates as claimed in claims 3-12, wherein said first organic solvent comprises from about 4% to about 50% and preferably from about 16 % to about 50 % by weight of the compositions.
14. The emulsifiable concentrates as claimed in claims 3-13, wherein the said second organic solvent having a dielectric constant from about 1 to about
4 is selected from toluene, xylene, solvesso-200, C-9, solvesso-100 and solvesso-150.
15. The emulsifiable concentrates as claimed in claims 3-14, wherein said second organic solvent is xylene.
16. The emulsifiable concentrates as claimed in claims 3-15 wherein said second organic solvent comprises from about 4 % to about 40 %, more preferably from about 8% to about 30% by weight of the compositions.
17. The emulsifiable concentrates as claimed in claims 3-16 wherein said first and second organic solvents comprise from about 10% to about 70% by total weight of the composition.
18. The emulsifiable concentrates as claimed in claims 3-17 wherein said first and second organic solvents are utilized in a weight ratio of from about 4: 1 to about 0.04 :1.
19. The emulsifiable concentrates as claimed in claims 3-18 comprising said first and second organic solvents, wherein said combination of said first and second solvents is selected such that the resultant εmiX is from about 4 to about 35, preferably from about 4 to about 23.
20. The emulsifiable concentrates as claimed in claims 3-19 additionally comprising at least one emulsifying agent selected from a group comprising lignosulphonates, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, non-ionic polyethoxylates, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, calcium salts of alkyl benzene sulphonates, salts of sulfonated naphthalene, styrenated phenol ethoxylate, castor oil ethoxylate, calcium dodecyl benzene sulphonate, sodium tetrapropylene benzenesulfonate, sodium 6- dodecylbenzenesulfonate, ammonium salts of sulfonated naphthalene, nonyl phenol ethoxylate, salts of polyacrylic acids and salts of phenol sulfonic acids.
21. The emulsifiable concentrates as claimed in 3-20, wherein said emulsifying agent is used in an amount from about 0.1 to about 40.0 %, preferably in an amount from about 1.0 to about 30.0 % and more preferably in an amount of about 2.0 to about 20.0 % by total weight of the compositions.
22. The emulsifϊable concentrates as claimed in claims 3-22 additionally comprising at least one stabilizer.
23. The emulsifiable concentrates as claimed in claims 3-22, wherein said stabilizer is selected from the group comprising butanol, propanol, propargyl alcohol, acetic anhydride, acetic acid, epichlorohydrin and epoxidised soybean oil.
24. The emulsifϊable concentrates as claimed in claims 3-23 wherein said stabilizer is used in an amount of about 0.25% to about 10% by total weight of the composition.
25. The emulsifiable concentrates as claimed in claims 3-25 having a pH range of from about 4.0 to about 6.0.
26. The composition as claimed in claims 3-25 additionally comprising at least one safener.
27. The composition as claimed in claim 26 wherein said safener is cloquintocet-mexyl.
28. The composition as claimed in claim 3-28 wherein said safener is present in an amount of about 0.1% to about 30%, more preferably about 1% to about 15% by weight of clodinafop acid or an agrochemically acceptable salt or an ester thereof.
29. A storage stable agrochemical emulsifiable concentrate comprising acifluorfen sodium in an amount of about 16.5 % by weight of the composition, Clodinafop propargyl in an amount of about 8 % by weight of the composition, a first organic solvent having a dielectric constant of 18.2, a second organic solvent having a dielectric constant of 2.5; wherein the ratio of said first and second organic solvents is about 2: 1 by weight, at least one emulsifying agent or mixtures thereof in an amount of about 15 % by weight of the composition, and at least one stabilizer in an amount of about 1 % by weight of the composition.
30. A process for preparing a storage stable agrochemical emulsifiable concentrate comprising (a) admixing at least a first organic solvent having a dielectric constant of from about 12 to about 50 and at least a second organic solvent having a dielectric constant of from about 1 to about 4 in a mixing vessel; (b) adding an agrochemically effective amount of acifluorfen sodium or fomesafen sodium and an agrochemically effective amount of clodinafop propargyl to the first homogenous mixture of step (a) at an ambient temperature to obtain second homogenous mixture; (c) adding at least one emulsifying agent in an amount of from about 0.1% to about 40% and at least one stabilizer in an amount of from about 0.25% to about 10% by weight of the composition to the second homogenous mixture of step (b) with stirring to obtain a homogenous mixture and; d) filtering the resultant mixture.
PCT/IN2010/000396 2009-06-12 2010-06-10 Herbicidal composition Ceased WO2010143205A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201080035114.XA CN102458131B (en) 2009-06-12 2010-06-10 Herbicidal compositions comprising acifluorfen sodium

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
IN1416MU2009 2009-06-12
IN1418/MUM/2009 2009-06-12
IN1416/MUM/2009 2009-06-12
IN1417/MUM/2009 2009-06-12
IN1417MU2009 2009-06-12
IN1418MU2009 2009-06-12

Publications (3)

Publication Number Publication Date
WO2010143205A2 true WO2010143205A2 (en) 2010-12-16
WO2010143205A3 WO2010143205A3 (en) 2011-05-19
WO2010143205A4 WO2010143205A4 (en) 2011-08-04

Family

ID=43099743

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2010/000396 Ceased WO2010143205A2 (en) 2009-06-12 2010-06-10 Herbicidal composition

Country Status (3)

Country Link
CN (1) CN102458131B (en)
TW (1) TW201101999A (en)
WO (1) WO2010143205A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022259259A1 (en) * 2021-06-08 2022-12-15 Aviral Crop Science Pvt. Ltd. Synergistic herbicidal composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4063929A (en) 1973-02-12 1977-12-20 Rohm And Haas Company Herbicidal 4-trifluoromethyl-4'nitrodiphenyl ethers
US4285723A (en) 1978-01-19 1981-08-25 Imperial Chemical Industries Limited Selective herbicides
US4713109A (en) 1981-12-31 1987-12-15 Ciba Geigy Corporation 2-(4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy)-propionic acid-propynyl ester with herbicidal activity
US6369001B1 (en) 1999-08-11 2002-04-09 Monsanto Technology, Llc Microemulsion coformulation of a graminicide and a water-soluble herbicide

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2510103A1 (en) * 1981-07-27 1983-01-28 Rhone Poulenc Agrochimie HERBICIDE COMPOUNDS DERIVED FROM PHENOXYBENZOIC ACIDS
CA1276647C (en) * 1984-12-12 1990-11-20 Teruyuki Misumi 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-a- substituted-acetophenone, oxime derivative thereof, process for preparing thereof, herbicidal composition, and method for the destruction of undesirable weeds
TR200100101T2 (en) * 1998-07-16 2001-06-21 Aventis Cropscience Gmbh Herbicide drugs.
WO2008138740A1 (en) * 2007-05-09 2008-11-20 Basf Se A method for controlling aquatic weeds using acifluorfen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4063929A (en) 1973-02-12 1977-12-20 Rohm And Haas Company Herbicidal 4-trifluoromethyl-4'nitrodiphenyl ethers
US4285723A (en) 1978-01-19 1981-08-25 Imperial Chemical Industries Limited Selective herbicides
US4713109A (en) 1981-12-31 1987-12-15 Ciba Geigy Corporation 2-(4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy)-propionic acid-propynyl ester with herbicidal activity
US6369001B1 (en) 1999-08-11 2002-04-09 Monsanto Technology, Llc Microemulsion coformulation of a graminicide and a water-soluble herbicide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF AGRICULTURE AND FOOD CHEMISTRY, vol. 31, no. 4, 1983, pages 751 - 755
WEED SCIENCE, vol. 37, 1989, pages 743 - 747

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022259259A1 (en) * 2021-06-08 2022-12-15 Aviral Crop Science Pvt. Ltd. Synergistic herbicidal composition

Also Published As

Publication number Publication date
TW201101999A (en) 2011-01-16
WO2010143205A4 (en) 2011-08-04
CN102458131A (en) 2012-05-16
WO2010143205A3 (en) 2011-05-19
CN102458131B (en) 2016-03-23

Similar Documents

Publication Publication Date Title
EP3319442B1 (en) Method for controlling herbicide resistant or tolerant weeds
RU2632968C2 (en) Herbicidal compositions containing 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-metoxyphenyl)pyridine-2-carboxylic acid or its derivative and synthetic auxin herbicide
JP5735517B2 (en) Low volatility amine salts of anionic pesticides
RU2632860C2 (en) Herbicidal compositions containing 4-amino-3-chloro-5-fluorine-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carbonic acid or its derivative and protoporphyrinogen oxidase inhibitor
RU2632491C2 (en) HERBICID COMPOSITIONS CONTAINING 4-AMINO-3-CHLORO-5-FLUORINE-6-(4-CHLORO-2-FLUORO-3-METHOXYPHENYL)PYRIDINE-2-CARBONIC ACID OR ITS DERIVATIVES AND ACETYL-COA CARBOXYLASE (ACCase) INHIBITOR
RU2629217C2 (en) Herbicidal compositions containing 4-amino-3-chloro-5-fluorine-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carbonic acid
CN105828615B (en) Synergistic herbicidal weed control
JP2020055817A (en) Synergistic weed control from the application of penoxyslam and benzobicyclon or clomazone and benzobicyclon
AU2022203163B2 (en) A process of controlling weeds
TW200944127A (en) Herbicidal compositions comprising pyroxasulfone
HK1212860A1 (en) Synergistic weed control from applications of aminocyclopyrachlor and triclopyr
JP2022003076A (en) How to control herbicide-resistant or resistant weeds
TWI755382B (en) Use of safeners with ppo inhibitor herbicides
CN108430221B (en) Herbicidal composition
MX2015000245A (en) Highly concentrated aqueous formulation comprising an anionic pesticide and a base.
WO2010143205A2 (en) Herbicidal composition
BR102020006625A2 (en) HERBICID MIXTURES AND FORMULATIONS
US20230404078A1 (en) Herbicidal combinations
SK65798A3 (en) New herbicidal compositions containing 4-benzoylisoxazoles and aclonifen
WO2025088604A1 (en) Composition containing polyelectrolyte solution and polycationic rheology modifier
CN111357756A (en) Weeding composition
WO2022259259A1 (en) Synergistic herbicidal composition
CN114828630A (en) Herbicidal composition
CN113271775A (en) Safened compositions comprising phenoxy herbicide and cloquintocet-mexyl for use in cereal crops and methods thereof
EA041573B1 (en) METHOD OF CONTROL WITH RESISTANT OR HERBICIDE TOLERANT WEEDS

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080035114.X

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10747689

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10747689

Country of ref document: EP

Kind code of ref document: A2