WO2021115494A1 - Nouvelles formes cristallines de flufénacet, leurs procédés de préparation et leur utilisation - Google Patents

Nouvelles formes cristallines de flufénacet, leurs procédés de préparation et leur utilisation Download PDF

Info

Publication number
WO2021115494A1
WO2021115494A1 PCT/CN2021/072800 CN2021072800W WO2021115494A1 WO 2021115494 A1 WO2021115494 A1 WO 2021115494A1 CN 2021072800 W CN2021072800 W CN 2021072800W WO 2021115494 A1 WO2021115494 A1 WO 2021115494A1
Authority
WO
WIPO (PCT)
Prior art keywords
flufenacet
crystalline modification
crystalline
solvent system
composition
Prior art date
Application number
PCT/CN2021/072800
Other languages
English (en)
Inventor
James Timothy BRISTOW
Original Assignee
Jiangsu Rotam Chemistry Co., 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 Jiangsu Rotam Chemistry Co., Ltd filed Critical Jiangsu Rotam Chemistry Co., Ltd
Priority to EP21731371.7A priority Critical patent/EP4073049A4/fr
Publication of WO2021115494A1 publication Critical patent/WO2021115494A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C07D285/13—Oxygen atoms
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides

Definitions

  • the present invention relates to novel crystalline forms of N- (4-Fluorophenyl) -N-isopropyl-2- ⁇ [5- (trifluoromethyl) -1, 3, 4-thiadiazol-2-yl] oxy ⁇ acetamide (flufenacet) . Further, the present invention relates to methods for the preparation of the novel crystalline forms of flufenacet. Still further, the present invention relates to the use of the crystalline forms of flufenacet in agrochemical preparations and for the control of unwanted plant growth.
  • N- (4-Fluorophenyl) -N-isopropyl-2- ⁇ [5- (trifluoromethyl) -1, 3, 4-thiadiazol-2-yl] oxy ⁇ acetamide having the common name flufenacet, is an oxyacetamide herbicide, highly effective against a wide range of broadleaf and grassy weeds.
  • Flufenacet has the molecular formula C 14 H 13 F 4 N 3 O 2 S and its chemical structure can be represented as follows:
  • Flufenacet and formulations containing flufenacet are available commercially. However, it has been found that the commercially available flufenacet exhibits a significant toxicity toward the aquatic species, such as fish. Therefore, there is a need to improve the performance of flufenacet and render flufenacet more environmentally acceptable, in particular to decrease the toxicity of flufenacet to animals, such as aquatic species of animals.
  • crystalline modification II flufenacet can exist in a crystalline form, herein termed “crystalline modification II” , which has been found to exhibit a lower toxicity toward aquatic species of animals. This lower toxicity provides significant advantages when using flufenacet in the crystalline modification II when preparing agrochemical formulations and the use thereof in the control of unwanted plant growth.
  • crystalline modification has the same meaning with the term “crystalline form” .
  • the present invention provides a crystalline modification II of flufenacet, the crystalline modification exhibiting at least three of the following reflexes, in any combination, as 2 ⁇ 0.2 degree in an X-ray powder diffractogram (XRD) recorded using Cu-K ⁇ radiation at 25 °C:
  • XRD X-ray powder diffractogram
  • the crystalline modification II of flufenacet according to the first aspect of the invention exhibits the following reflexes:
  • the crystalline modification II of flufenacet according to the first aspect of the invention exhibits the following reflexes:
  • the crystalline modification II of flufenacet according to the first aspect of the invention exhibits the following reflexes:
  • the crystalline modification II of flufenacet according to the first aspect of the invention exhibits the following reflexes:
  • the present invention provides a crystalline modification II of flufenacet, the crystalline modification exhibiting an infrared (IR) spectrum with characteristic functional group vibration peaks at wavenumbers (cm -1 , ⁇ 0.2%) of one or more of 1676.95, 1484.76, 1309.70, 1151.70, 1033.94 and 943.23 cm -1 .
  • IR infrared
  • the present invention provides a crystalline modification II of flufenacet, the crystalline modification exhibiting a melting point of from 77.1°C.
  • a crystalline modification II of flufenacet exhibiting a differential scanning calorimetry (DSC) profile having an endothermic melting peak with onset at 76.0°C and peak maximum at 77.1°C, more preferably with a melting enthalpy of 65.43 J/g.
  • DSC differential scanning calorimetry
  • the crystalline modification II of flufenacet is useful in controlling plant growth. Accordingly, the present invention also provides compositions for controlling plant growth, such as weeds, comprising the crystalline modification II of flufenacet.
  • flufenacet may be employed on its own, as a mixture with auxiliaries and carriers and/or as a mixture with other active compounds.
  • the present invention provides the use of the crystalline modification II of flufenacet in the control of undesirable plant growth.
  • the present invention provide a method for controlling plant growth at a locus, the method comprising applying to the locus the crystalline modification II of flufenacet.
  • Figure 1 is an X-ray powder diffraction (XRD) spectrum of the crystalline modification II of flufenacet;
  • Figure 2 is an infrared (IR) spectrum of the crystalline modification II of flufenacet.
  • Figure 3 is a Differential Scanning Calorimetry (DSC) spectrum of the crystalline modification II of flufenacet.
  • the crystalline modification II of flufenacet is readily comminuted and/or ground. This facilitates the preparation of a wide range of agrochemical formulations, such as suspension concentrates (SC) , oil-based suspension concentrates (OD) , water-dispersible granules (WG) and water-soluble granules (SG) .
  • SC suspension concentrates
  • OD oil-based suspension concentrates
  • WG water-dispersible granules
  • SG water-soluble granules
  • the crystalline modification II of flufenacet may be characterized as exhibiting at least three of the following reflexes, in any combination, as 2 ⁇ 0.2 degree in an X-ray powder diffractogram (XRD) recorded using Cu-K ⁇ radiation at 25 °C:
  • XRD X-ray powder diffractogram
  • the crystalline modification II of flufenacet of the present invention is characterized by an X-ray powder diffractogram having at least three of the reflexes indicated above.
  • the crystalline modification II of flufenacet is one having at least four of the aforementioned reflexes, more preferably at least five of the aforementioned reflexes, still more preferably six, more preferably still seven, especially eight of the aforementioned reflexes, again in any combination thereof.
  • the crystalline modification II of flufenacet exhibits at least three, more preferably four, still more preferably five, more preferably still six, especially seven, of the following reflexes, in any combination, as 2 ⁇ 0.2 degree in an X-ray powder diffractogram (XRD) recorded using Cu-K ⁇ radiation at 25°C:
  • XRD X-ray powder diffractogram
  • the crystalline modification II of flufenacet exhibits all of the following reflexes, in any combination, as 2 ⁇ 0.2 degree in an X-ray powder diffractogram (XRD) recorded using Cu-K ⁇ radiation at 25°C:
  • a preferred crystalline modification II of flufenacet exhibits all of the reflexes listed above, in particular all of the reflexes (1) to (13) .
  • the X-ray powder diffractogram of the crystalline modification II of flufenacet shown in Figure 1 was taken using a diffractometer with a reflection geometry in the range from 3° to 60° with increments of 0.03° using Cu-Ka radiation at 25°C.
  • the present invention provides a crystalline modification II of flufenacet exhibiting an infrared (IR) spectrum with characteristic functional group vibration peaks at wavenumbers (cm -1 , ⁇ 0.2%) of one or more of the following: 1676.95, 1484.76, 1309.70, 1151.70, 1033.94 and 943.23 cm -1 .
  • IR infrared
  • a preferred crystalline modification II of flufenacet exhibits an infrared (IR) spectrum with characteristic functional group vibration peaks at wavenumbers (cm -1 , ⁇ 0.2%) of two or more, preferably three or more, more preferably four of the following: 1676.95, 1484.76, 1309.70, 1151.70, 1033.94 and 943.23 cm -1 .
  • a preferred crystalline modification II of flufenacet exhibits an infrared (IR) spectrum with characteristic functional group vibration peaks at wavenumbers (cm -1 , ⁇ 0.2%) having all of the aforementioned vibration peaks.
  • the crystalline modification II of flufenacet exhibits an X-ray powder diffractogram as described above for the first aspect of the invention and an infrared (IR) spectrum as described above for the second aspect of the present invention.
  • a third aspect of the present invention provides a crystalline modification II of flufenacet, exhibiting a melting point of about 77.1°C.
  • the crystalline modification II of flufenacet exhibits a melting point of about 77.1°C according to this third aspect of the invention, together with an X-ray powder diffractogram as described above for the first aspect of the invention and/or an infrared (IR) spectrum as described above for the second aspect of the present invention.
  • a fourth aspect of the present invention provides a crystalline modification II of flufenacet exhibiting a differential scanning calorimetry (DSC) profile having an endothermic melting peak with onset at 76.0°C and peak maximum at 77.1°C, more preferably with a melting enthalpy of 65.43 J/g.
  • DSC differential scanning calorimetry
  • the crystalline modification II of flufenacet exhibits a differential scanning calorimetry (DSC) profile having an endothermic melting peak with onset at 76.0°Cand peak maximum at 77.1°C according to this fourth aspect of the invention, together with an X-ray powder diffractogram as described above for the first aspect of the invention and/or an infrared (IR) spectrum as described above for the second aspect of the present invention and/or a melting point as described above for the third aspect of the present invention.
  • DSC differential scanning calorimetry
  • the crystalline modification II of flufenacet is characterized by an X-ray powder diffraction pattern substantially as shown in Figure 1, and/or characterized by an IR spectrum substantially as shown in Figure 2, and/or characterized by a DSC thermogram substantially as shown in Figure 3, and/or by a melting point of about 77.1°C.
  • Flufenacet is available commercially. Methods for preparing flufenacet are well known in the art. One particularly suitable method for preparing flufenacet is described in US 4,968,342.
  • the present invention provides a method for preparing a crystalline modification II of flufenacet, the method comprising the steps of:
  • the solution of flufenacet may be provided in step i) by heating flufenacet in the solvent system while stirring until dissolved completely.
  • the form of flufenacet used in this step may be any form of flufenacet other than the crystalline modification II.
  • flufenacet heated in the solvent system in step i) is amorphous flufenacet.
  • the solvent system employed in the method is one in which flufenacet is readily soluble and is one from which the crystalline modification II of flufenacet is crystallised. In this respect, it has been found that appropriate selection of the solvent system is required in order to yield flufenacet in the crystalline modification II.
  • the solvent system yielding the crystalline modification II of flufenacet comprises one or more solvents selected from aliphatic, cycloaliphatic or aromatic hydrocarbons, cymene, petroleum fractions, and petroleum ether.
  • Suitable aliphatic hydrocarbon solvents are known in the art.
  • Preferred aliphatic hydrocarbon solvents include alkanes, more preferably C 5 to C 10 alkanes, especially C 5 to C 9 alkanes, for example pentane, hexane, heptane, octane and nonane.
  • the aliphatic hydrocarbon solvents may be straight chained or branched, with straight chain or normal hydrocarbons being preferred, for example n-pentane, n-hexane, n-heptane, n-octane and n-nonane.
  • Suitable cycloaliphatic hydrocarbon solvents are known in the art and include cycloalkanes, preferably C 5 to C 8 cycloalkanes.
  • the cycloalkanes may be substituted, for example bearing one or more substituents, such as C 1 to C 4 alkyl-substituted cycloalkanes, especially cycloalkanes bearing one or more methyl substituents.
  • Preferred cycloaliphatic hydrocarbon solvents include cyclohexane and substituted-cyclohexane, for example methylcyclohexane.
  • aromatic hydrocarbon solvents are known in the art.
  • the aromatic hydrocarbons may bear one or more substituents, such as one or more C 1 to C 4 alkyl moieties.
  • Preferred aromatic hydrocarbon solvents are benzene and derivatives of benzene, such as cymene, toluene and xylene.
  • Suitable petroleum fractions for use as solvents are known in the art.
  • Preferred petroleum fractions are those having a boiling point of from 50 to 200°C, more preferably from 60 to 190°C, such as ligroin or heavy naphtha having a boiling point of from 90 to 140°C or light naphtha having a boiling point from 60 to 80°C.
  • One particularly preferred solvent is xylene.
  • the present invention provides the use of a solvent system to prepare crystalline flufenacet having reduced toxicity, wherein the solvent system comprises one or more solvents selected from aliphatic, cycloaliphatic or aromatic hydrocarbons, petroleum fractions, and petroleum ether.
  • the solvent system may consist essentially of a single solvent selected from the aforementioned solvents.
  • the solvent system may comprise a mixture of two or more of the aforementioned solvents, for example a mixture of three or four solvents.
  • a solution of flufenacet in the solvent system is provided.
  • the solvent system may be heated to a temperature above room temperature, for example to a temperature from 25°C, more preferably to a temperature from 30°C.
  • the solvent system may be heated to a temperature up to the boiling point of the solvent system, preferably up to 90°C, more preferably up to 80°C, still more preferably up to 70°C, more preferably still up to 60°, depending upon the solvent system being employed.
  • the solvent system may be heated to a temperature of from 30 to 60°C.
  • the flufenacet is preferably combined with the solvent system while stirring until the flufenacet starting material is dissolved completely.
  • step ii) of the method flufenacet is caused to precipitate from the solution to yield the crystalline modification II of flufenacet. Any suitable technique for precipitating flufenacet from the solution provided in step i) may be used.
  • the solution of flufenacet in the solvent system is cooled.
  • the solution may be cooled to any suitable temperature to cause the crystalline modification II of flufenacet to crystallise out of the solution.
  • the solution may be cooled to a temperature of down to -20°C, preferably down to -15°C.
  • the solution may be cooled to a temperature of up to 10°C, more preferably up to 5°C. Cooling to a temperature in the range of from -15 to 5°C is preferred for many embodiments.
  • precipitation may be facilitated by removing solvent from the solution, for example by applying a vacuum to the solution.
  • seed crystals are added to the solution.
  • the addition of seed crystals facilitates precipitation of the solute from the solution, as is known in the art.
  • the seed crystals are crystals of flufenacet, more preferably crystals of the crystalline modification II of flufenacet.
  • the amount of seed crystals added to the solution is typically in the range of from 0.001 to 10% by weight, preferably from 0.001% to 2.5% by weight, more preferably from 0.005 to 0.5%by weight, based on the weight of flufenacet present in the solution provided in step i) .
  • the seed crystals are preferably added to the solution at a temperature below the boiling point of the solvent system.
  • step iii) of the method the precipitated crystalline modification II of flufenacet is isolated or recovered from the solvent system. Any suitable technique may be used to recover the crystalline modification II of flufenacet, for example filtration, centrifugation and/or decantation.
  • the isolated solid flufenacet is preferably washed one or more times with a solvent system comprising one or more solvents.
  • the solvent system employed in the washing stage comprises one or more components of the solvent system of the solution provided in step (i) , as described hereinbefore. Washing is preferably carried out using the solvent system at a temperature from 0°C to room temperature, depending on the solubility of the crystalline form of flufenacet in the solvent, in order to minimize or avoid the loss of crystalline material in the corresponding washing solvent.
  • flufenacet as an herbicide is known in the art and is used on a commercial scale. It has been found that the crystalline modification II of flufenacet is also active in controlling undesirable plant growth, such as weeds. Techniques of formulating and applying amorphous flufenacet are known in the art, for example as disclosed in the prior art documents described hereinbefore. These techniques can also be applied in an analogous manner to the crystalline modification II of flufenacet.
  • the present invention further provides a herbicidal composition comprising the crystalline modification II of flufenacet as defined hereinbefore.
  • the herbicidal composition generally comprises one or more auxiliary components, as described in more detail hereinafter.
  • the herbicidal composition may comprise the crystalline modification II of flufenacet in any suitable amount, which may depend upon such factors as the type of formulation being employed.
  • the composition comprises the crystalline modification II of flufenacet in an amount of from 5% by weight of the composition, preferably from 10% by weight of the composition, more preferably from 20%by weight of the composition.
  • the composition comprises the crystalline modification II of flufenacet in an amount of about 50% by weight of the composition.
  • the composition may be formulated in any suitable form.
  • the composition is in the form of a suspension concentrate (SC) , an oil-based suspension concentrate (OD) , water-soluble granules (SG) , a dispersible concentrate (DC) , an emulsifiable concentrate (EC) , an emulsion seed dressing, a suspension seed dressing, granules (GR) , microgranules (MG) , a suspoemulsion (SE) or water-dispersible granules (WG) .
  • SC suspension concentrate
  • OD oil-based suspension concentrate
  • DC dispersible concentrate
  • EC emulsifiable concentrate
  • emulsion seed dressing emulsion seed dressing
  • GR granules
  • MG microgranules
  • SE suspoemulsion
  • WG water-dispersible granules
  • the composition is in the form of a suspension concentrate (SC) .
  • the composition is in the form of water-dispersible granules (WG) .
  • compositions are prepared by combining the crystalline modification II of flufenacet with one or more agriculturally acceptable auxiliaries.
  • auxiliaries employed in the composition and their amounts will depend upon the type of formulation and/or the manner in which the formulation is to be applied by the end user.
  • Suitable auxiliaries are customary formulation adjuvant or components, such as dispersants, wetting agents, emulsifiers, extenders, carriers, solvents, surfactants, stabilizers, anti-foam agents, anti-freeze agents, preservatives, antioxidants, colourants, thickeners, solid adherents and inert fillers.
  • Such auxiliaries are known in the art and are commercially available. Their use in the formulation of the compositions of the present invention will be apparent to the person skilled in the art.
  • Surfactants can be an emulsifier, dispersant or wetting agent of ionic or nonionic type.
  • Examples which may be used include, but are not limited to, salts of polyacrylic acids, salts of lignosulphonic acid, salts of phenylsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, especially alkylphenols, sulphosuccinic ester salts, taurine derivatives, especially alkyltaurates, or phosphoric esters of polyethoxylated phenols or alcohols.
  • Liquid diluents include, but are not limited to, water, N, N-dimethylamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, paraffins, alkylbenzenes, alkyl naphthalenes, glycerine, triacetine, oils of olive, castor, linseed, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as hexyl acetate, heptyl acetate and octyl acetate, and alcohols such methanol, cyclohexanol, decanol, benzyl and tetrahydrofurfuryl alcohol, and mixtures thereof.
  • the composition may further comprise one or more polymeric stabilizers.
  • Suitable polymeric stabilizers that may be used in the present invention include, but are not limited to, polypropylene, polyisobutylene, polyisoprene, copolymers of monoolefins and diolefins, polyacrylates, polystyrene, polyvinyl acetate, polyurethanes or polyamides. Suitable stabilizers are known in the art and are commercially available.
  • the composition may further comprise one or more anti-foam agents.
  • Suitable anti-foam agents include those substances which can normally be used for this purpose in agrochemical compositions and will be readily apparent to the person skilled in the art. Suitable anti-foam agents are known in the art and are commercially available. Particularly preferred anti-foam agents are mixtures of polydimethylsiloxanes and perfluroalkylphosphonic acids, such as the silicone anti-foam agents (for example commercially available from GE or Compton) . Other examples of anti-foam agents are fatty acids, tallow, and sodium salts.
  • the composition may further comprise one or more preservatives.
  • Suitable preservatives include those substances which can normally be used for this purpose in agrochemical compositions of this type and again are well known in the art. Suitable examples that may be mentioned include (commercially available from Bayer AG) and (commercially available from Bayer AG) .
  • the composition may further comprise one or more antioxidants.
  • Suitable antioxidants are substances which can normally be used for this purpose in agrochemical compositions, as is known in the art. Preference is given, for example, to butylated hydroxytoluene.
  • the composition may further comprise one or more solid adherents.
  • adherents are known in the art and available commercially.
  • Suitable solid adherents include organic adhesives, including tackifiers, such as celluloses of substituted celluloses, natural and synthetic polymers in the form of powders, granules, or lattices, and inorganic adhesives such as gypsum, silica, or cement.
  • the composition may further comprise one or more inert fillers.
  • inert fillers are known in the art and available commercially. Suitable fillers include, for example, natural ground minerals, such as kaolins, aluminas, talc, chalk, quartz, attapulgite, montmorillonite, and diatomaceous earth, or synthetic ground minerals, such as highly dispersed silicic acid, aluminum oxide, silicates, and calcium phosphates and calcium hydrogen phosphates.
  • Suitable inert fillers for granules include, for example, crushed and fractionated natural minerals, such as calcite, marble, pumice, sepiolite, and dolomite, or synthetic granules of inorganic and organic ground materials, as well as granules of organic material, such as sawdust, coconut husks, corn cobs, and tobacco stalks.
  • inert fillers also include sodium tripolyphosphate and sucrose.
  • Solid diluents can be water-soluble or water-insoluble.
  • Water-soluble solid diluents include, but are not limited to, salts such as alkali metal phosphates (for example sodium dihydrogen phosphate) , alkaline earth phosphates, sulfates of sodium, potassium, magnesium and zinc, sodium and potassium chloride, sodium acetate, sodium carbonate and sodium benzoate, and sugars and sugar derivatives such as sorbitol, lactose, sucrose and mannitol.
  • Examples of water-insoluble solid diluents include, but are not limited to clays, synthetic and diatomaceous silicas, calcium and magnesium silicates, titanium dioxide, aluminum, calcium and zinc oxide, and mixtures thereof.
  • Wetting agents include, but are not limited to, alkyl sulfosuccinates, laureates, alkyl sulfates, phosphate esters, acetylenic diols, ethoxyfluornated alcohols, ethoxylated silicones, alkyl phenol ethyoxylates, benzene sulfonates, alkyl-substituted benzene sulfonates, alkyl a-olefin sulfonates, naphthalene sulfonates, alkyl-substituted naphthalene sulfonates, condensates of naphthalene sulfonates and alkyl-substituted naphthalene sulfonates with formaldehyde, and alcohol ethoxylates, and mixtures thereof. Alkyl naphthalene sulphonates, sodium salts are particularly useful for the composition
  • Dispersants include, but are not limited to, sodium, calcium and ammonium salts of ligninsulfonates (optionally polyethoxylated) ; sodium and ammonium salts of maleic anhydride copolymers; sodium salts of condensed phenolsulfonic acid; and naphthalene sulfonate-formaldehyde condensates.
  • Ligninsulfonates such as sodium ligninsulfonates are particularly useful for the composition of the invention.
  • Naphthalene sulfonate-formaldehyde condensates such as naphthalenesulfonic acid, polymers with formaldehyde, and sodium salts are particularly useful for the composition of the invention.
  • Thickening agents include, but are not limited to, guar gum, pectin, casein, carrageenan, xanthan gum, alginates, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose, and mixtures thereof.
  • Synthetic thickening agents include derivatives of the former categories, and also polyvinyl alcohols, polyacrylamides, polyvinylpyrrolidones, various polyethers, their copolymers, as well as polyacrylic acids and their salts, and mixtures thereof. Alkylpolyvinylpyrrolidones are particularly useful for the composition of the invention.
  • formulation components can also be used in the present invention such as dyes, drying agents, and the like. These components and their uses are known to one skilled in the art.
  • composition of the present invention may comprise the crystalline modification II of flufenacet as the sole active ingredient.
  • active components such as attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers, semiochemicals, insecticides or agents for improving plant properties.
  • the present invention also provides a method for controlling unwanted plant growth, comprising applying to the plant, plant part, or surroundings of the plant, a herbicidally effective amount of the crystalline modification II of flufenacet as hereinbefore described.
  • the crystalline modification II of flufenacet is preferably applied in the form of a composition as hereinbefore described.
  • compositions of the present invention are known in the art and will be understood by the person skilled in the art. Techniques include diluting or dispersing the composition in a suitable diluent or carrier liquid, in particular water, and applying the composition by spraying.
  • plants are to be understood as meaning all plants and plant populations such as desired and undesired wild plants or crop plants, including naturally occurring crop plants.
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods, by biotechnological and genetic engineering methods, or by combinations of these methods, including the transgenic plants and the plant cultivars which may or may not be protected by plant breeders' rights.
  • Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoots, leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.
  • Harvested materials, and vegetative and generative propagation materials for example, cuttings, tubers, meristem tissue, rhizomes, offsets, seeds, single and multiple plant cells and any other plant tissues, are also included.
  • compositions or formulations of the invention can be carried out directly or by allowing the compositions or formulations to act on their surroundings, habitat or storage space by the customary treatment methods known in the art.
  • customary treatment methods include dipping, spraying, vaporizing, fogging, broadcasting, painting on in the case of propagation material, and applying one or more coats particularly in the case of seeds.
  • the benefits of the present invention are particularly advantageous when the crystalline modification II of flufenacet or its herbicidal composition are applied to kill weeds in crops of useful plants, such as cereals, for example wheat, barley, rye, oats, maize, rice, sorghum, triticale and related crops; fruit, such as pomes, stone fruit and soft fruit, such as apples, grapes, pears, plums, peaches, almonds, pistachio, cherries, and berries, for example strawberries, raspberries and blackberries, bell pepper, red pepper; leguminous plants, for example beans, lentils, peas and soybeans; oil plants, such as rape, mustard and sunflowers; cucurbitaceae, such as marrows, cucumbers and melons; fiber plants, for example cotton, flax, hemp and jute; citrus, such as calamondin, citrus citron, citrus hybrids, including chironja, tangelo and tangor, grapefruit, kumquat,
  • the invention may be used to control a wide range of undesired plants, including broadleaf plants and grassy weeds.
  • the broadleaf weeds include such plants as shepherds purse (Capsella bursapastories) , fat hen (Chenopodium album) , double thorn (Oxygonum sinuatum) , black bind weed (Polygonum convolvulus) , Mexican marigold (Tagetes minuta) , gallant soldier (Galinsogo parviflora) , and white charlock (Raphanus raphanastrium) .
  • the grassy weeds include such plants as foxtail (Setaria spp. ) , wild finder millet (Eleusine spp. ) , couch grass (Digitaria spp. ) and rye grass (Lolium spp. ) .
  • references to properties are, unless stated otherwise, to properties measured under ambient conditions, i.e. at atmospheric pressure and at a temperature of about 20°C.
  • the term “about” or “around” when used in connection with a numerical amount or range means somewhat more or somewhat less than the stated numerical amount or range, and for example to a deviation of ⁇ 10% of the stated numerical amount or endpoint of the range.
  • “Surrounding, ” as used herein, refers to the place on which the plants are growing, the place on which the plant propagation materials of the plants are sown or the place on which the plant propagation materials of the plants will be sown.
  • Precipitation refers to the sedimentation of a solid material (a precipitate) , including the sedimentation of a crystalline material, from a liquid solution in which the solid material is present in amounts greater than its solubility in the amount of liquid solution.
  • herbicidally effective amount refers to the quantity of such a compound or combination of such compounds that is capable of producing a controlling effect on the growth of plants.
  • the controlling effects include all deviation from the natural development of the target plants, for example killing, retardation of one or more aspects of the development and growth of the plant, leaf burn, albinism, dwarfing and the like.
  • Flufenacet was prepared generally in accordance with the method of Example 1 of US 4,968,342, as follows:
  • the solid flufenacet product was isolated by filtering with suction. Flufenacet obtained was amorphous.
  • Flufenacet prepared in Example 1 (10 g) was placed in a 3 neck round bottom flask, together with xylene (60 mL) . The resulting mixture was heated to a temperature of from 30 to 60°C while stirring until the flufenacet had dissolved completely. Thereafter, the solution was slowly cooled to a temperature of from -15°C to 5°C. Upon cooling, fine crystals formed. The slurry of crystals and solution was stirred at room temperature for 2 hours. Thereafter, the slurry was filtered and washed with xylene (3 mL) . The filtered crystals were dried under a vacuum at room temperature in order to remove the xylene traces from the crystalline product.
  • the crystalline product thus obtained had a purity of >98% and the product recovered as crystals was found to be not less than 80% yield.
  • the crystal product was analyzed by IR spectrometry, XRD and DSC and found to be crystalline modification II of flufenacet as shown in Figures 1, 2 and 3, respectively.
  • the IR spectrum of the crystalline flufenacet exhibited the functional group characteristic vibrations peaks at wavenumbers of one or more of about 1676.95, 1484.78, 1309.70, 1151.70, 1033.94 and 943.23 cm -1 , as shown in Figure 2.
  • DSC Differential scanning calorimetry
  • a suspension concentrate (SC) formulation was prepared as follows:
  • Example 2 To provide a comparison, the procedure of Example 2 above was followed to prepare crystalline flufenacet using a range of different solvents.
  • the solvent employed in each case is indicated in Table 3 below.
  • Copepods (A clausi) were placed in culture vessels (2.5 L plastic buckets) and maintained at 14 ⁇ 1°C in a temperature-controlled room under conditions of dim light, with a photoperiod of 14 hours light and 10 hours dark.
  • test end point was immobility of the animal, identified by a lack of movement when gently prodded or blown with a stream of water.
  • Acute EC50 values were calculated using Probit or Spearman-Karber analyses using Tox Calc.
  • the crystalline modification II of flufenacet exhibits a significantly lower toxicity than amorphous flufenacet and other crystalline forms of flufenacet.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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

L'invention concerne une nouvelle modification cristalline II de flufénacet, caractérisée par un diffractogramme de rayons X sur poudre (XRD), un spectre infrarouge (IR), un point de fusion et/ou un profil de calorimétrie différentielle à balayage (DSC). L'invention concerne également un procédé de préparation de la modification cristalline II de flufénacet comprenant : i) la fourniture d'une solution de flufénacet dans un système de solvant comprenant un ou plusieurs solvants; ii) la précipitation de la modification cristalline II de flufénacet à partir de la solution; et iii) l'isolement de la modification cristalline II précipitée de flufénacet. L'invention concerne en outre des compositions comprenant la modification cristalline II de flufénacet et l'utilisation de la modification cristalline II dans la lutte contre la croissance de plantes indésirables.
PCT/CN2021/072800 2019-12-13 2021-01-20 Nouvelles formes cristallines de flufénacet, leurs procédés de préparation et leur utilisation WO2021115494A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP21731371.7A EP4073049A4 (fr) 2019-12-13 2021-01-20 Nouvelles formes cristallines de flufénacet, leurs procédés de préparation et leur utilisation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1918401.9A GB2592888A (en) 2019-12-13 2019-12-13 Novel crystalline forms of Flufenacet, methods for their preparation and use of the same
GB1918401.9 2019-12-13

Publications (1)

Publication Number Publication Date
WO2021115494A1 true WO2021115494A1 (fr) 2021-06-17

Family

ID=69186830

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/072800 WO2021115494A1 (fr) 2019-12-13 2021-01-20 Nouvelles formes cristallines de flufénacet, leurs procédés de préparation et leur utilisation

Country Status (3)

Country Link
EP (1) EP4073049A4 (fr)
GB (1) GB2592888A (fr)
WO (1) WO2021115494A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113575577A (zh) * 2021-08-17 2021-11-02 京博农化科技有限公司 一种用于制备悬浮剂的助剂组合、氟噻草胺水悬浮剂及其制备方法
EP4073050A4 (fr) * 2019-12-13 2024-01-03 Jiangsu Rotam Chemistry Co Ltd Nouvelles formes cristallines de flufénacet, son procédé de préparation et son utilisation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5852202A (en) * 1997-12-12 1998-12-22 Bayer Corporation Process for isolating N-(4-fluorophenyl)-N-(1-methylethyl)-2- (5-trifluoromethyl)-1,3,4-thiadiazol-2-yl)oxy!acetamide
CN1224007A (zh) * 1997-12-12 1999-07-28 美国拜尔公司 制备噻二唑乙酰胺类衍生物化合物的方法
CN1134424C (zh) * 1997-12-12 2004-01-14 美国拜尔公司 应用质子惰性芳族溶剂制备噻二唑乙酰胺类衍生物化合物的方法
CN103664824A (zh) * 2013-11-19 2014-03-26 泸州东方农化有限公司 噻二唑酰胺类化合物的制备方法
CN105646397A (zh) * 2014-11-27 2016-06-08 孙智华 一种氟噻草胺的制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3821600A1 (de) * 1988-06-27 1989-12-28 Bayer Ag Heteroaryloxyessigsaeure-n-isopropylanilide
DK201300088U1 (da) * 2013-05-31 2013-07-12 Andersen Tine Et produkt med nyttige egenskaber
DK201300188U1 (da) * 2013-12-03 2013-12-13 Refsgaard Anne Marie Viktoria Kemisk forbindelse med nyttige egenskaber
EP3415506A1 (fr) * 2017-06-13 2018-12-19 Solvay Sa Procédé de fabrication de composés de thiadiazole à substitution haloalkyle
EP3415507A1 (fr) * 2017-06-13 2018-12-19 Solvay Sa Procédé de fabrication de composés d'acétamides aryl-thiadiazole
GB2589919A (en) * 2019-12-13 2021-06-16 Rotam Agrochem Int Co Ltd Novel crystalline forms of flufenacet, methods for their preparation and use of the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5852202A (en) * 1997-12-12 1998-12-22 Bayer Corporation Process for isolating N-(4-fluorophenyl)-N-(1-methylethyl)-2- (5-trifluoromethyl)-1,3,4-thiadiazol-2-yl)oxy!acetamide
CN1224007A (zh) * 1997-12-12 1999-07-28 美国拜尔公司 制备噻二唑乙酰胺类衍生物化合物的方法
CN1134424C (zh) * 1997-12-12 2004-01-14 美国拜尔公司 应用质子惰性芳族溶剂制备噻二唑乙酰胺类衍生物化合物的方法
CN1142924C (zh) * 1997-12-12 2004-03-24 美国拜尔公司 制备噻二唑乙酰胺类衍生物化合物的方法
CN103664824A (zh) * 2013-11-19 2014-03-26 泸州东方农化有限公司 噻二唑酰胺类化合物的制备方法
CN105646397A (zh) * 2014-11-27 2016-06-08 孙智华 一种氟噻草胺的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4073049A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4073050A4 (fr) * 2019-12-13 2024-01-03 Jiangsu Rotam Chemistry Co Ltd Nouvelles formes cristallines de flufénacet, son procédé de préparation et son utilisation
CN113575577A (zh) * 2021-08-17 2021-11-02 京博农化科技有限公司 一种用于制备悬浮剂的助剂组合、氟噻草胺水悬浮剂及其制备方法

Also Published As

Publication number Publication date
EP4073049A4 (fr) 2024-01-03
EP4073049A1 (fr) 2022-10-19
GB2592888A (en) 2021-09-15
GB201918401D0 (en) 2020-01-29

Similar Documents

Publication Publication Date Title
AU2021427503B2 (en) Novel crystalline form of pyroxasulfone, methods for its preparation and use of the same
TWI735574B (zh) 甲磺草胺（ｓｕｌｆｅｎｔｒａｚｏｎｅ）之新穎形式、其製備方法及用途
CN106243175B (zh) 一种制备甲氨基阿维菌素苯甲酸盐的新晶型的方法及其应用
WO2021115494A1 (fr) Nouvelles formes cristallines de flufénacet, leurs procédés de préparation et leur utilisation
US20170247354A1 (en) Novel form of rimsulfuron, a process for its preparation and use of the same
WO2017101515A1 (fr) Nouvelle forme de spirodiclofène, son procédé de préparation et son utilisation
WO2021115493A2 (fr) Nouvelles formes cristallines de flufénacet, son procédé de préparation et son utilisation
US10947181B2 (en) Crystalline form of tefluthrin, process for its preparation and use thereof
US9617247B1 (en) Form of halosulfuron-methyl, a process for its preparation and use of the same
WO2017092469A1 (fr) Nouvelle forme de tribénuron-méthyle, son procédé de préparation et son utilisation
US9643973B1 (en) Crystalline form of diclosulam, a process for its preparation and use of the same
CN111132966B (zh) 甲嘧磺隆的新形式、其制备方法及其用途
WO2023051311A1 (fr) Forme cristalline du diflufénicane, son procédé de préparation et son utilisation
AU2016265996A1 (en) A novel crystalline form of oxamyl, a process for its preparation and use of the same
US9663501B1 (en) Process for preparing a novel crystalline form of thifensulfuron-methyl and use of the same
US10077248B2 (en) Form of imazapyr, a process for its preparation and use the same
WO2023031810A1 (fr) Forme cristalline de florasulame, sa préparation et son utilisation
EP4114817A1 (fr) Nouvelle forme de métrafénone, son procédé de préparation et son utilisation
BR102019017785A2 (pt) Forma de sulfometuron-metílico, processo para sua preparação e uso da mesma

Legal Events

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

Ref document number: 21731371

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021731371

Country of ref document: EP

Effective date: 20220713