WO2018153707A1 - Crystalline forms of a strobilurin type compound for combating phytopathogenic fungi - Google Patents

Crystalline forms of a strobilurin type compound for combating phytopathogenic fungi Download PDF

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Publication number
WO2018153707A1
WO2018153707A1 PCT/EP2018/053378 EP2018053378W WO2018153707A1 WO 2018153707 A1 WO2018153707 A1 WO 2018153707A1 EP 2018053378 W EP2018053378 W EP 2018053378W WO 2018153707 A1 WO2018153707 A1 WO 2018153707A1
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crystalline form
pent
pyrazol
oxy
enamide
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PCT/EP2018/053378
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French (fr)
Inventor
Joachim Rheinheimer
Martin Viertelhaus
Thorsten Jabs
Wassilios Grammenos
Ana Escribano Cuesta
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Definitions

  • the present invention relates to crystalline forms of the strobilurin-type compound
  • Strobilurin type compounds for combating phytopathogenic fungi resistant to Qo inhibitors have been described in WO 2013/092224; WO 2014/202421 and EP 2815650 A1. It had been found that certain strobilurin-type compounds have antifungal activity against phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, especially wherein the mutation in the mitochondrial cytochrome b gene of the phytopathogenic fungi is G143A.
  • Qo inhibitor includes any substance that is capable of diminishing and/or inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bc1 complex in mitochondria.
  • the oxidation center is typically located on the outer side of the inner mito- chrondrial membrane.
  • a range of active substances can exist in different crystalline but also in amorphous modifications. Polymorphism is the term used in these cases.
  • a polymorph is a solid, crystalline phase of a compound which is characterized by a specific, uniform packing and arrangement of the molecules in the solid.
  • Different modifications of one and the same compound can sometimes have different proper- ties, for example differences in the following properties: solubility, vapor pressure, dissolution rate, stability against a phase change into a different modification, stability during grinding, suspension stability, optical and mechanical properties, hygroscopicity, crystal form and size, filter- ability, density, melting point, stability to decomposition, color and sometimes even chemical reactivity or biological activity.
  • the present invention relates to a novel crystalline form of compound (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide of formula I
  • a powder X-ray diffraction diagram using Cu- ⁇ radiation at 25 °C shows at least the peaks, given as 2 ⁇ values: 6.8°, 9.4° and 13.6° within an error marigin of ⁇ 0.2° 2 ⁇ .
  • Said crystalline form is herein called crystalline form A or form A.
  • This crystalline form A can be identified by powder X-ray diffractometry (PXRD) on the basis of its diffraction diagram (see peaks in Figure 1 denoted with 2 ⁇ values: 6.8, 9.4 and 13.6).
  • PXRD powder X-ray diffractometry
  • a PXRD diagram of form A recorded using Cu- ⁇ radiation at 25 °C shows at least the peaks, given as 2 ⁇ values: 6.8°, 9.4° and 13.6° within an error marigin of ⁇ 0.2° 2 ⁇ .
  • a PXRD diagram of form A recorded using Cu- ⁇ radiation at 25 °C shows at least the peaks, given as 2 ⁇ values: 6.8°, 9.4° and 13.6° within an error marigin of ⁇ 0.1 ° 2 ⁇ .
  • a PXRD diagram of form A recorded using Cu- ⁇ radiation at 25 °C shows at least the peaks, given as 2 ⁇ values: 6.8°, 9.4° and 13.6° within an error marigin of ⁇ 0.05° 2 ⁇ .
  • a Differential Scanning Calorimetry (DSC) analysis of the crystalline form A displays a thermogram with a melting peak characterized by an onset temperature in the range from 95 to 1 14°C.
  • the onset temperature of the melting peak typically lies in the range from about 95°C to 1 14°C, preferably in the range of 100°C to 1 12°C, more preferably in the range from 103°C to 1 10°C and in particular in the range from 105°C to 108°C.
  • the values quoted here relate to values determined by DSC using aluminum pans, heating rate 10°C/min as described herein later.
  • a DSC analysis of the crystalline form A displays a thermogram with a melting peak characterized alternatively by a peak temperature in the range from 100 to 1 15°C.
  • the peak temperature of the melting peak typically lies in the range from about 100°C to 1 15°C, preferably in the range of 105°C to 1 14°C, more preferably in the range from 104°C to 1 1 1 °C and in particular in the range from 106°C to 1 10°C.
  • the values quoted here relate to values determined by DSC using aluminum pans, heating rate 10°C/min as described herein later.
  • a further embodiment relates to a crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol- 3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide, which, in a powder X-ray diffractogram using Cu-K Q radiation at 25°C, shows at least the following three peaks, given as 2 ⁇ values with an error margin of 0.2° 2 ⁇ : 6.8°, 9.4° and 13.6°, or which, in a DSC curve measured by a differential scanning calorimeter at a scan rate of 10°C per minute, exhibits an endothermic peak with an onset temperature in the range of 95°C to 1 14°C.
  • the present invention relates to another another crystalline form of compound (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-en- amide of formula I
  • crystalline form B a powder X-ray diffraction diagram using Cu- ⁇ radiation at 25 °C shows at least the peaks, given as 2 ⁇ values: 1 1 .6°, 15.7° and 18.9° within an error marigin of ⁇ 0.2° 2 ⁇ .
  • Said crystalline form is herein called crystalline form B or form B.
  • This crystalline form B according to the invention can be identified by PXRD on the basis of its diffraction diagram (see marked peaks in Figure 3).
  • a PXRD diagram of form B recorded using Cu- ⁇ radiation at 25 °C shows at least 3 and especially all of the peaks, given as 2 ⁇ values: 6.2°, 1 1.6°, 15.7°, 17.6°, 18.9° and 23.9° within an error marigin of ⁇ 0.2° ⁇ .
  • a PXRD diagram of form B recorded using Cu- ⁇ radia- tion at 25 °C shows at least 3 and especially all of the peaks, given as 2 ⁇ values: 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9° within an error marigin of ⁇ 0.1 ° 2 ⁇ .
  • a PXRD diagram of form B recorded using Cu- ⁇ radiation at 25 °C shows at least 3 and especially all of the peaks, given as 2 ⁇ values: 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9° within an error marigin of ⁇ 0.05° ⁇ .
  • a PXRD diagram of form B recorded using Cu- ⁇ radiation at 25 °C shows at least 3, preferably at least 5, in particular at least 7, and especially all of the peaks, given as 2 ⁇ values: 6.2°, 1 1.6°, 12.8°, 15.4°, 15.7°, 16.0°, 17.6°, 18.9°, 22.8°, 23.9°, 24.4°, 25.2°, 26.0° and 31.7° within an error marigin of ⁇ 0.2° 2 ⁇ .
  • a PXRD diagram of form B recorded using Cu- Ka radiation at 25 °C shows at least 3, preferably at least 5, in particular at least 7, and espe- daily all of the peaks, given as 2 ⁇ values: 6.2°, 1 1 .6°, 12.8°, 15.4°, 15.7°, 16.0°, 17.6°, 18.9°, 22.8°, 23.9°, 24.4°, 25.2°, 26.0° and 31 .7° within an error marigin of ⁇ 0.1 ° 2 ⁇ .
  • a PXRD diagram of form B recorded using Cu- ⁇ radiation at 25 °C shows at least 3, preferably at least 5, in particular at least 7, and especially all of the peaks, given as 2 ⁇ values: 6.2°, 1 1 .6°, 12.8°, 15.4°, 15.7°, 16.0°, 17.6°, 18.9°, 22.8°, 23.9°, 24.4°, 25.2°, 26.0° and 31 .7° within an er- ror marigin of ⁇ 0.05° 2 ⁇ .
  • a DSC analysis of the crystalline form B displays a thermogram with a melting peak charac- teristised by an onset temperature in the range from 1 15 to 130°C.
  • the onset temperature of the melting peak typically lies in the range from about 1 15°C to 130°C, preferably in the range of 1 18°C to 128°C, more preferably in the range from 120°C to 128°C and in particular in the range from 120°C to 126°C.
  • the values quoted here relate to values determined by DSC using aluminum pans, heating rate 10°C/min as described herein later.
  • a DSC analysis of the crystalline form B displays a thermogram with a melting peak charac- teristised alternatively by a peak temperature in the range from 1 15 to 130°C.
  • the peak temperature of the melting peak typically lies in the range from about 1 15°C to 130°C, preferably in the range of 120°C to 128°C, more preferably in the range from 121 °C to 128°C and in particular in the range from 123°C to 127°C.
  • the values quoted here relate to values determined by DSC using aluminum pans, heating rate 10°C/min as described herein later.
  • a further embodiment relates to a crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol- 3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide, which, in a powder X-ray diffractogram using Cu-K Q radiation at 25°C, shows at least three of the six following peaks, given as 2 ⁇ values with an error margin of 0.2° 2 ⁇ : 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9°, or which, in a DSC curve measured by a differential scanning calorimeter at a scan rate of 10°C per minute, exhibits an endothermic peak with an onset temperature in the range of 1 15°C to 130°C.
  • the present invention relates to a crystalline form B of (Z,2E)-5-[1 -(2,4-dichlo- rophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide (i.e. compound I), which, in a powder X-ray diffractogram using Cu- ⁇ radiation at 25°C, shows at least three of the six following peaks, given as 2 ⁇ values with an error marigin of ⁇ 0.2° 2 ⁇ : 6.3°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9°.
  • the present invention relates to a crystalline form B of (Z,2E)-5-[1 -(2,4-di- chlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide (i.e. compound I), which, in a powder X-ray diffractogram using Cu- ⁇ radiation at 25°C, shows the six following peaks, given as 2 ⁇ values with an error marigin of ⁇ 0.2° 2 ⁇ : 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9°.
  • the present invention relates to a crystalline form B of (Z,2E)-5-[1 -(2,4- dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide (i.e. compound I), which, in a powder X-ray diffractogram using Cu- ⁇ radiation at 25°C, shows the 14 following peaks, given as 2 ⁇ values with an error marigin of ⁇ 0.2° 2 ⁇ : 6.2°, 1 1 .6°, 12.8°, 15.4°, 15.7°, 16.0°, 17.6°, 18.9°, 22.8°, 23.9°, 24.4°, 25.2°, 26.0° and 31.7°.
  • the compounds (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-di- methyl-pent-3-enamide of formula I may also called compound I herein.
  • the ability of a substance to exist in more than one crystalline form is generally referred to as polymorphism and the different "crystalline forms” are also named “polymorphs" and may be characterized by certain analytical properties such as their PXRD patterns or their DSC curves measured by a differ- ential scanning calorimeter.
  • the crystalline forms which are described herein, are essentially free from solvent, which means that the crystalline forms comprise no detectable amounts of solvents incorporated into the crystal lattice, i.e. in the 3-dimensional crystal lattice, wherein the molecules are positioned.
  • the amount of solvent in the crystal lattice is less than 10 mol%, preferably less than 5 mol%, more preferably less than 1 mol% based on compound I.
  • the intensity of the peaks is typically plotted versus the 2 ⁇ angle to obtain a diffractogram.
  • Such a diffractogram typically shows at least 2, preferably at least 4, more preferably at least 6, still more preferably at least 7, particularly preferably at least 10 peaks.
  • the 2 ⁇ values which can be determined from the diffractogram and which are provided herein, often represent approximate values within an error margin in the range of from 0.1 ° 2 ⁇ to 0.4° 2 ⁇ , preferably from 0.1 to
  • a 2 ⁇ value of, e.g., 7.01 may be understood as a 2 ⁇ value of 7.01 ° ⁇ 0.2°, prefera- bly 7.01 ° ⁇ 0.1 °, more preferably 7.01 ° ⁇ 0.05°, particularly preferably exactly 7.01 °.
  • DSC curves as provided herein can be obtained using a differential scanning calorimeter (e.g. a Mettler Toledo DSC 823e module DSC823e/700/229) under nitrogen stream at a scan rate of 10°C per minute, wherein the sample is heated in aluminum pans. The heat flux is then plotted versus the temperature.
  • the exothermic and endothermic peaks which can be meas- ured, represent, e.g., crystallization or recrystallization processes (exothermic) or melting processes (endothermic).
  • the peaks are typically defined by their onset temperature, i.e. the temperature, at which an exothermic or endothermic process begins, and their peak temperature,
  • Mixtures of two crystalline forms may be identified by comparing the recorded 2 ⁇ values and DSC curves with the respective data of pure crystalline forms. If the diffractogram shows characteristic peaks of both crystalline forms, it can be concluded that a mixture of the two crystalline forms is present.
  • compounds containing impurities usually melt at lower temperature than the pure compound. In fact, it can melt over a wide range of temperatures. This effect is called the "melting point depression".
  • the present invention also relates in one embodiment to the use of crystalline form A of compound I as a fungicide for combating phytopathogenic fungi.
  • the present invention relates to the use of crystalline form B of compound I as a fungicide for combating phytopathogenic fungi.
  • the present invention relates in one embodi- ment to a methoid for combating phytopathogenic fungi, comprising: treating the phytopathogenic fungi as defined in herein or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined herein with an effective amount of crystalline form A and/or B of compound I, in particular of form B of compound I.
  • the present invention also relates to plant propagation material, comprising crystalline form A or form B of compound I or a mixture of crystalline forms A and B as defined herein in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation material.
  • plant propagation material comprising crystalline form A or form B of compound I or a mixture of crystalline forms A and B as defined herein in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation material.
  • Preferred weight ratios of crystalline form B to crystalline form A in such mixtures may e.g. be in the range of from 60:40 to 40:60 or from 10:90 to 40:60 or from 90:10 to 60:40.
  • an amorphous form is only present in such mixtures in minor amounts, e.g. in an amount of less than 10 wt.-% or less than 5 wt.-% based on the total weight of the mixture, or not contained in the mixtures at all.
  • the crystalline form B, the crystalline form A, and the mixtures of crystalline form B with crys- talline form A of compound I are suitable for controlling fungal diseases of plants caused by phytopathogenic fungi. Specific crops and their fungal diseases are listed, e.g., in
  • the present invention relates to the use of a mixture of crystalline form B and crystalline form A as a pesticide for controlling phytopathogenic fungi.
  • the crystalline form B or a mixture thereof with crystalline form A of compound I can be converted into customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • customary formulations for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the mixtures according to the invention.
  • the invention also relates to agrochemical compositions comprising at least one auxiliary and crystalline form B or a mixture thereof with crystalline form A of compound I as defined above.
  • An agrochemical composition comprises a pesticidally effective amount of crystalline form B as defined herein or a mixture thereof with crystalline form A of compound I.
  • effective amount denotes an amount of crystalline form B or a mixture as defined above by referring the total amount of compound I, said amount being sufficient for controlling harmful pests on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants.
  • Such an amount can vary in a broad range and is dependent on various factors, such as the animal pests' species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific mixture used.
  • compositions e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries Suitable auxiliaries, solvents, liquid carriers, solid carriers, fillers, surfactants, adjuvants, thickeners, bactericides, anti-foaming agents, colorants and tackifiers, which may be used in the context of the agrochemical compositions can be found, e.g., in WO 2013/092224.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of crystalline form B or a mixture thereof with crystalline form A of compound I, based on the total weight of the composition.
  • the compound I is employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • a suspension concentration is preferred for the application in crop protection.
  • the SC agrochemical composition comprises between 50 to 500 g/L (grams per Liter), or between 100 and 250 g/L, or 100 g/L or 150g/L or 200g/L or 250 g/L of crystalline form B or a mixture thereof with other forms as defined herein.
  • Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. Details in this regard may also be found in WO 2013/092224.
  • Crystalline form B of compound I and mixtures thereof with crystalline form A of compound I may be applied as disclosed for similar compounds in WO 2013/092224.
  • Preferred is the application on crops.
  • Specific crops as well as typical fungal diseases to be controlled in connection with these crops are disclosed e.g. in WO 2013/092224.
  • the crystalline forms are used to control those phytopathogenic fungi which contain a mutation in the mitochondrial cyto- chrome b gene conferring resistance to Qo inhibitors, wherein the mutation is G143A.
  • phytopathogneic fungi are selected from the group consisting of Alternaria al- ternata, Blumeria graminis, Magnaporthe grisea (anamorph: Pyricularia oryzae), Mycosphaer- ella graminicola (anamorph: Septoria tritici), Mycosphaerella fijiensis, Venturia inaequalis, Pyre- nophora teres, Pyrenophona tritici-repentis (anamorph: Drechslera tritici-repentis) and Plasmo- para viticola, in particular Mycosphaerella graminicola.
  • the inventin relates to a method for combating phytopathogenic fungi, comprising: treating the phytopathogenic fungi as defined herein or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined herein with an effective amount of at least one crystalline form as defined herien, or a composi- tion comprising it thereof. More preferably, this method comprises a) identifying the phytopathogenic fungi as defined herein, and b) treating said fungi or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined herein with an effective amount of at least one crystalline form as defined herein, or a composition comprising it thereof.
  • Seed treatment is particularly preferred.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, mate- rials or rooms by the phytopathogenic fungi. Additional details in this regard are provided in
  • the crystalline form B and the mixtures thereof with form A of compound I according to the invention may also be applied for the protection of materials such as wood against fungal patho- gens.
  • the crystalline forms and their mixtures according to the invention are preferably used as described WO 2013/092224 for compound I and related compounds.
  • DSC was performed on a Mettler Toledo DSC 823e/700/229 module.
  • the samples were placed in aluminum standard pans.
  • the sample size in each case was 1 to 10 mg.
  • the heating rate was 10°C/min.
  • the samples were purged with a stream of nitrogen during the experiment.
  • the melting point was determined as the extrapolated peak onset temperature (also called on- set temperature, often abbreviated as T m , T e or T 0 ) defined by the point of intersection of the tangent at the half height of the melting peak, on the principal side of the peak with the linelarily extrapolated initial base line.
  • T p peak temperature
  • SC-XRD Single crystal X-ray diffraction
  • Example P1 Preparation of a mixture of crystalline forms A and B of Compound I
  • the PXRD pattern of the obtained mixture of crystalline form A and B, measured using Cu- Ka radiation at 25°C, is shown in Figure 1.
  • a PXRD pattern of the crystalline form A shows at least the following peaks, given as 2 ⁇ values: 6.8, 9.4 and 13.6.
  • Example P2 Preparation of crystalline form B of Compound I
  • the complete DSC curve is shown in Figure 4.
  • the crystalline form B has been characterised further by single crystal X-ray diffratometry (SC-XRD) at a temperature of 100 K. It was found that the crystalline form is triclinic.
  • the detailed unit cell parameters from the SC-XRD investigation using a single crystal diffracto meter from Bruker are shown in Table 1 .
  • Table 1 Crystallographic data of crystalline form B.
  • Table 2 Atom positions within the unit cell of crystalline form B.
  • FIG. 1 Asymmetric unit of crystalline form B of compound I (the numbering of the atoms is according to the nomenclature in Table 2).

Abstract

The present invention relates to crystalline forms of the strobilurin-type compound (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-N,3-dimethyl-pent-3-enamide and to processes for their preparation and agrochemical compositions comprising these crystalline forms.

Description

Crystalline forms of a strobilurin type compound for combating phytopathogenic fungi Description
The present invention relates to crystalline forms of the strobilurin-type compound
(Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide and to processes for their preparation and agrochemical compositions comprising these crystalline forms.
Strobilurin type compounds for combating phytopathogenic fungi resistant to Qo inhibitors have been described in WO 2013/092224; WO 2014/202421 and EP 2815650 A1. It had been found that certain strobilurin-type compounds have antifungal activity against phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, especially wherein the mutation in the mitochondrial cytochrome b gene of the phytopathogenic fungi is G143A.
"Qo inhibitor," as used herein, includes any substance that is capable of diminishing and/or inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bc1 complex in mitochondria. The oxidation center is typically located on the outer side of the inner mito- chrondrial membrane.
The compound (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dime- thyl-pent-3-enamide depicted below, and will be referred to as compound I in the following:
Figure imgf000002_0001
has been disclosed with its 1H-NMR data as compound 1-15 in WO 2013/092224.
A range of active substances can exist in different crystalline but also in amorphous modifications. Polymorphism is the term used in these cases. A polymorph is a solid, crystalline phase of a compound which is characterized by a specific, uniform packing and arrangement of the molecules in the solid.
Different modifications of one and the same compound can sometimes have different proper- ties, for example differences in the following properties: solubility, vapor pressure, dissolution rate, stability against a phase change into a different modification, stability during grinding, suspension stability, optical and mechanical properties, hygroscopicity, crystal form and size, filter- ability, density, melting point, stability to decomposition, color and sometimes even chemical reactivity or biological activity.
It has now surprisingly been found that by applying suitable preparation and crystallization conditions stable crystalline modifications (herein also called crystalline forms) of compound I can be prepared. These crystalline forms are hereinafter described and termed form A and form B, respectively.
In a first aspect, the present invention relates to a novel crystalline form of compound (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide of formula I
Figure imgf000003_0001
which is characterized by at least one the following characteristics:
a) a melting point of from 95 to 1 14°C;
b) a powder X-ray diffraction diagram using Cu-Κα radiation at 25 °C shows at least the peaks, given as 2Θ values: 6.8°, 9.4° and 13.6° within an error marigin of ± 0.2° 2Θ.
Said crystalline form is herein called crystalline form A or form A.
This crystalline form A can be identified by powder X-ray diffractometry (PXRD) on the basis of its diffraction diagram (see peaks in Figure 1 denoted with 2Θ values: 6.8, 9.4 and 13.6). Thus, a PXRD diagram of form A recorded using Cu-Κα radiation at 25 °C shows at least the peaks, given as 2Θ values: 6.8°, 9.4° and 13.6° within an error marigin of ± 0.2° 2Θ. More preferably, a PXRD diagram of form A recorded using Cu-Κα radiation at 25 °C shows at least the peaks, given as 2Θ values: 6.8°, 9.4° and 13.6° within an error marigin of ± 0.1 ° 2Θ. In particular, a PXRD diagram of form A recorded using Cu-Κα radiation at 25 °C shows at least the peaks, given as 2Θ values: 6.8°, 9.4° and 13.6° within an error marigin of ± 0.05° 2Θ.
A Differential Scanning Calorimetry (DSC) analysis of the crystalline form A displays a thermogram with a melting peak characterized by an onset temperature in the range from 95 to 1 14°C. The onset temperature of the melting peak typically lies in the range from about 95°C to 1 14°C, preferably in the range of 100°C to 1 12°C, more preferably in the range from 103°C to 1 10°C and in particular in the range from 105°C to 108°C. The values quoted here relate to values determined by DSC using aluminum pans, heating rate 10°C/min as described herein later.
A DSC analysis of the crystalline form A displays a thermogram with a melting peak characterized alternatively by a peak temperature in the range from 100 to 1 15°C. The peak temperature of the melting peak typically lies in the range from about 100°C to 1 15°C, preferably in the range of 105°C to 1 14°C, more preferably in the range from 104°C to 1 1 1 °C and in particular in the range from 106°C to 1 10°C. The values quoted here relate to values determined by DSC using aluminum pans, heating rate 10°C/min as described herein later.
A further embodiment relates to a crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol- 3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide, which, in a powder X-ray diffractogram using Cu-KQ radiation at 25°C, shows at least the following three peaks, given as 2Θ values with an error margin of 0.2° 2Θ: 6.8°, 9.4° and 13.6°, or which, in a DSC curve measured by a differential scanning calorimeter at a scan rate of 10°C per minute, exhibits an endothermic peak with an onset temperature in the range of 95°C to 1 14°C.
In a second aspect, the present invention relates to another another crystalline form of compound (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-en- amide of formula I
Figure imgf000004_0001
which is characterized by at least one the following characteristics:
c) a melting point of from 100 to 120°C;
d) a powder X-ray diffraction diagram using Cu-Κα radiation at 25 °C shows at least the peaks, given as 2Θ values: 1 1 .6°, 15.7° and 18.9° within an error marigin of ± 0.2° 2Θ. Said crystalline form is herein called crystalline form B or form B. This crystalline form B according to the invention can be identified by PXRD on the basis of its diffraction diagram (see marked peaks in Figure 3).
Thus, a PXRD diagram of form B recorded using Cu-Κα radiation at 25 °C shows at least 3 and especially all of the peaks, given as 2Θ values: 6.2°, 1 1.6°, 15.7°, 17.6°, 18.9° and 23.9° within an error marigin of ± 0.2°θ. Preferably, a PXRD diagram of form B recorded using Cu-Κα radia- tion at 25 °C shows at least 3 and especially all of the peaks, given as 2Θ values: 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9° within an error marigin of ± 0.1 ° 2Θ. More preferably, a PXRD diagram of form B recorded using Cu-Κα radiation at 25 °C shows at least 3 and especially all of the peaks, given as 2Θ values: 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9° within an error marigin of ± 0.05°θ.
Thus, a PXRD diagram of form B recorded using Cu-Κα radiation at 25 °C shows at least 3, preferably at least 5, in particular at least 7, and especially all of the peaks, given as 2Θ values: 6.2°, 1 1.6°, 12.8°, 15.4°, 15.7°, 16.0°, 17.6°, 18.9°, 22.8°, 23.9°, 24.4°, 25.2°, 26.0° and 31.7° within an error marigin of ± 0.2° 2Θ. Preferably, a PXRD diagram of form B recorded using Cu- Ka radiation at 25 °C shows at least 3, preferably at least 5, in particular at least 7, and espe- daily all of the peaks, given as 2Θ values: 6.2°, 1 1 .6°, 12.8°, 15.4°, 15.7°, 16.0°, 17.6°, 18.9°, 22.8°, 23.9°, 24.4°, 25.2°, 26.0° and 31 .7° within an error marigin of ± 0.1 ° 2Θ. More preferably, a PXRD diagram of form B recorded using Cu-Κα radiation at 25 °C shows at least 3, preferably at least 5, in particular at least 7, and especially all of the peaks, given as 2Θ values: 6.2°, 1 1 .6°, 12.8°, 15.4°, 15.7°, 16.0°, 17.6°, 18.9°, 22.8°, 23.9°, 24.4°, 25.2°, 26.0° and 31 .7° within an er- ror marigin of ± 0.05° 2Θ. A DSC analysis of the crystalline form B displays a thermogram with a melting peak charac- teristised by an onset temperature in the range from 1 15 to 130°C. The onset temperature of the melting peak typically lies in the range from about 1 15°C to 130°C, preferably in the range of 1 18°C to 128°C, more preferably in the range from 120°C to 128°C and in particular in the range from 120°C to 126°C. The values quoted here relate to values determined by DSC using aluminum pans, heating rate 10°C/min as described herein later.
A DSC analysis of the crystalline form B displays a thermogram with a melting peak charac- teristised alternatively by a peak temperature in the range from 1 15 to 130°C. The peak temperature of the melting peak typically lies in the range from about 1 15°C to 130°C, preferably in the range of 120°C to 128°C, more preferably in the range from 121 °C to 128°C and in particular in the range from 123°C to 127°C. The values quoted here relate to values determined by DSC using aluminum pans, heating rate 10°C/min as described herein later.
A further embodiment relates to a crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol- 3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide, which, in a powder X-ray diffractogram using Cu-KQ radiation at 25°C, shows at least three of the six following peaks, given as 2Θ values with an error margin of 0.2° 2Θ: 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9°, or which, in a DSC curve measured by a differential scanning calorimeter at a scan rate of 10°C per minute, exhibits an endothermic peak with an onset temperature in the range of 1 15°C to 130°C. In one aspect, the present invention relates to a crystalline form B of (Z,2E)-5-[1 -(2,4-dichlo- rophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide (i.e. compound I), which, in a powder X-ray diffractogram using Cu-Κα radiation at 25°C, shows at least three of the six following peaks, given as 2Θ values with an error marigin of ± 0.2° 2Θ: 6.3°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9°.
In another aspect, the present invention relates to a crystalline form B of (Z,2E)-5-[1 -(2,4-di- chlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide (i.e. compound I), which, in a powder X-ray diffractogram using Cu-Κα radiation at 25°C, shows the six following peaks, given as 2Θ values with an error marigin of ± 0.2° 2Θ: 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9°.
In a further aspect, the present invention relates to a crystalline form B of (Z,2E)-5-[1 -(2,4- dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide (i.e. compound I), which, in a powder X-ray diffractogram using Cu-Κα radiation at 25°C, shows the 14 following peaks, given as 2Θ values with an error marigin of ± 0.2° 2Θ: 6.2°, 1 1 .6°, 12.8°, 15.4°, 15.7°, 16.0°, 17.6°, 18.9°, 22.8°, 23.9°, 24.4°, 25.2°, 26.0° and 31.7°.
Further embodiments of the present invention can be found in the claims, the description and the examples. It is to be understood that the features mentioned above and those still to be illustrated below of the subject matter of the invention can be applied not only in the respective given combination but also in other combinations without leaving the scope of the invention.
In the context of the present invention, the terms, which are used, are each defined as follows: The compound (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-di- methyl-pent-3-enamide of formula I may also called compound I herein. The ability of a substance to exist in more than one crystalline form is generally referred to as polymorphism and the different "crystalline forms" are also named "polymorphs" and may be characterized by certain analytical properties such as their PXRD patterns or their DSC curves measured by a differ- ential scanning calorimeter. Preferably, the crystalline forms, which are described herein, are essentially free from solvent, which means that the crystalline forms comprise no detectable amounts of solvents incorporated into the crystal lattice, i.e. in the 3-dimensional crystal lattice, wherein the molecules are positioned. In particular, the amount of solvent in the crystal lattice is less than 10 mol%, preferably less than 5 mol%, more preferably less than 1 mol% based on compound I.
PXRD data as provided herein can be obtained using a Panalytical X'pert Pro diffractometer (manufacturer: Panalytical) in reflection geometry in the range of 2Θ = 3°-40° with increments of 0.017° using Cu-Κα radiation (1 .5418 A) at 25°C. The intensity of the peaks is typically plotted versus the 2Θ angle to obtain a diffractogram. Such a diffractogram typically shows at least 2, preferably at least 4, more preferably at least 6, still more preferably at least 7, particularly preferably at least 10 peaks. The skilled person will understand that the 2Θ values, which can be determined from the diffractogram and which are provided herein, often represent approximate values within an error margin in the range of from 0.1 ° 2Θ to 0.4° 2Θ, preferably from 0.1 to
0.2° 2Θ. Thus, a 2Θ value of, e.g., 7.01 may be understood as a 2Θ value of 7.01 °±0.2°, prefera- bly 7.01 °±0.1 °, more preferably 7.01 °±0.05°, particularly preferably exactly 7.01 °.
DSC curves as provided herein can be obtained using a differential scanning calorimeter (e.g. a Mettler Toledo DSC 823e module DSC823e/700/229) under nitrogen stream at a scan rate of 10°C per minute, wherein the sample is heated in aluminum pans. The heat flux is then plotted versus the temperature. The exothermic and endothermic peaks, which can be meas- ured, represent, e.g., crystallization or recrystallization processes (exothermic) or melting processes (endothermic). The peaks are typically defined by their onset temperature, i.e. the temperature, at which an exothermic or endothermic process begins, and their peak temperature,
1. e. the temperature at the peak maximum or minimum.
Mixtures of two crystalline forms may be identified by comparing the recorded 2Θ values and DSC curves with the respective data of pure crystalline forms. If the diffractogram shows characteristic peaks of both crystalline forms, it can be concluded that a mixture of the two crystalline forms is present. However, compounds containing impurities usually melt at lower temperature than the pure compound. In fact, it can melt over a wide range of temperatures. This effect is called the "melting point depression".
Accordingly, the present invention also relates in one embodiment to the use of crystalline form A of compound I as a fungicide for combating phytopathogenic fungi. In another embodiment, the present invention relates to the use of crystalline form B of compound I as a fungicide for combating phytopathogenic fungi. Furthermore, the present invention relates in one embodi- ment to a methoid for combating phytopathogenic fungi, comprising: treating the phytopathogenic fungi as defined in herein or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined herein with an effective amount of crystalline form A and/or B of compound I, in particular of form B of compound I. The present invention also relates to plant propagation material, comprising crystalline form A or form B of compound I or a mixture of crystalline forms A and B as defined herein in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation material. In certain situations, it can be advantageous to provide mixtures of crystalline form B and crystalline form A of compound I; e.g. when it is desired to combine the advantageous properties of crystalline form B with the advantageous properties of crystalline form A. Preferred weight ratios of crystalline form B to crystalline form A in such mixtures may e.g. be in the range of from 60:40 to 40:60 or from 10:90 to 40:60 or from 90:10 to 60:40. It is preferred that an amorphous form is only present in such mixtures in minor amounts, e.g. in an amount of less than 10 wt.-% or less than 5 wt.-% based on the total weight of the mixture, or not contained in the mixtures at all.
The crystalline form B, the crystalline form A, and the mixtures of crystalline form B with crys- talline form A of compound I are suitable for controlling fungal diseases of plants caused by phytopathogenic fungi. Specific crops and their fungal diseases are listed, e.g., in
WO 2013/092224.
In another embodiment, the present invention relates to the use of a mixture of crystalline form B and crystalline form A as a pesticide for controlling phytopathogenic fungi.
The crystalline form B or a mixture thereof with crystalline form A of compound I can be converted into customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the mixtures according to the invention.
Therefore, the invention also relates to agrochemical compositions comprising at least one auxiliary and crystalline form B or a mixture thereof with crystalline form A of compound I as defined above.
An agrochemical composition comprises a pesticidally effective amount of crystalline form B as defined herein or a mixture thereof with crystalline form A of compound I. The term "effective amount" denotes an amount of crystalline form B or a mixture as defined above by referring the total amount of compound I, said amount being sufficient for controlling harmful pests on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the animal pests' species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific mixture used.
The crystalline form B and forma A as defined herein and the mixtures of crystalline form B with form A as defined herein can be converted into customary types of agrochemical compositions, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries, solvents, liquid carriers, solid carriers, fillers, surfactants, adjuvants, thickeners, bactericides, anti-foaming agents, colorants and tackifiers, which may be used in the context of the agrochemical compositions can be found, e.g., in WO 2013/092224.
Details regarding the preparation of the above mentioned types of agrochemical composi- tions may also be found in WO 2013/092224.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of crystalline form B or a mixture thereof with crystalline form A of compound I, based on the total weight of the composition. The compound I is employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
In one embodiment, a suspension concentration (SC) is preferred for the application in crop protection. In one sub-embodiment thereof, the SC agrochemical composition comprises between 50 to 500 g/L (grams per Liter), or between 100 and 250 g/L, or 100 g/L or 150g/L or 200g/L or 250 g/L of crystalline form B or a mixture thereof with other forms as defined herein. Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. Details in this regard may also be found in WO 2013/092224.
Crystalline form B of compound I and mixtures thereof with crystalline form A of compound I may be applied as disclosed for similar compounds in WO 2013/092224. Preferred is the application on crops. Specific crops as well as typical fungal diseases to be controlled in connection with these crops are disclosed e.g. in WO 2013/092224. Preferably, the crystalline forms are used to control those phytopathogenic fungi which contain a mutation in the mitochondrial cyto- chrome b gene conferring resistance to Qo inhibitors, wherein the mutation is G143A. More preferably, those phytopathogneic fungi are selected from the group consisting of Alternaria al- ternata, Blumeria graminis, Magnaporthe grisea (anamorph: Pyricularia oryzae), Mycosphaer- ella graminicola (anamorph: Septoria tritici), Mycosphaerella fijiensis, Venturia inaequalis, Pyre- nophora teres, Pyrenophona tritici-repentis (anamorph: Drechslera tritici-repentis) and Plasmo- para viticola, in particular Mycosphaerella graminicola.
According to a further embedment, the inventin relates to a method for combating phytopathogenic fungi, comprising: treating the phytopathogenic fungi as defined herein or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined herein with an effective amount of at least one crystalline form as defined herien, or a composi- tion comprising it thereof. More preferably, this method comprises a) identifying the phytopathogenic fungi as defined herein, and b) treating said fungi or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined herein with an effective amount of at least one crystalline form as defined herein, or a composition comprising it thereof.
Seed treatment is particularly preferred. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, mate- rials or rooms by the phytopathogenic fungi. Additional details in this regard are provided in
WO 2013/092224 for compound I and related compounds. They can be applied also to the crystalline forms according to the presenti invention.
The crystalline form B and the mixtures thereof with form A of compound I according to the invention may also be applied for the protection of materials such as wood against fungal patho- gens. For use against said pathogens causing destruction of materials, the crystalline forms and their mixtures according to the invention are preferably used as described WO 2013/092224 for compound I and related compounds.
The following figures and examples further illustrate the present invention.
Examples Analytical methods The powder X-ray diffractograms (PXRD) reported herein and displayed in Figures 1 and 3 were recorded using a Panalytical X'Pert Pro diffractometer (manufacturer: Panalytical) in reflection geometry (Bragg-Brantano) in the range from 2Θ = 3°- 40° with increments of e.g. 0.017° and measurement time of 20 s/step using Cu-Κα radiation (1 .5418 A) at room temperature (at about 25°C). The tube voltage was 45 kV and current 40 mA. The sample was placed in a sili- con single crystal sample holder of 0.2 mm depth and flattened.
DSC was performed on a Mettler Toledo DSC 823e/700/229 module. The samples were placed in aluminum standard pans. The sample size in each case was 1 to 10 mg. The heating rate was 10°C/min. The samples were purged with a stream of nitrogen during the experiment. The melting point was determined as the extrapolated peak onset temperature (also called on- set temperature, often abbreviated as Tm, Te or T0) defined by the point of intersection of the tangent at the half height of the melting peak, on the principal side of the peak with the linelarily extrapolated initial base line. In addition, the so-called peak temperature Tp was determined as described therein.
The Single crystal X-ray diffraction (SC-XRD) data were collected on a Bruker AXS 8D Pro- spector diffractometer at 100 K with Cu-Κα radiation (1 .5418 A). The images were processed with Saint (Bruker AXS) and the structure was solved with SHELXS and refined with SHELXL.
Preparation Examples
Example P1 : Preparation of a mixture of crystalline forms A and B of Compound I
P1.1 1 -(2, 4-Dichloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1 H-pyrazole The reaction has been carried out under a protective atmosphere of nitrogen. To 16.8 g (64.2 mmol) triphenylphosphine and 24.3 g (67.2 mmol) (Z)-3-tributyhstannanyl-but-2-en-1 -ol in 700 ml tetrahydrofurane (THF) have been added with stirring at about -70°C 13.6 g (67.2 mmol) azodicarbonic acid diisopropyl ester. The mixture has been stirred at this temperature for 5 min. After addition of 14.0 g (61 .2 mmol) 1 -(2, 4-dichlorophenyl)-3-hydroxypyrazole at about -70°C a red suspension was formed. The mixture was allowed to warm up to ambient temperature and stirred overnight. After removal of the solvents in vacuo the residue has been stirred with 500 ml of n-hexane and filtered. The solid residue was washed three times with n-hexane and the combined hexane solutions have been concentrated in vacuo to yield 40.1 g of crude product. Purifi- cation by chromatography on silica with heptane/ methyl-tert.-butylether (MTBE) 20:1 to 10:1. Yield 52.7 g of sufficient purity for the next reaction.
P1.2 (Z)-5-[1 -(2, 4-Dichloro-phenyl)-1 H-pyrazol-3-yloxy]-2-[(£)-methoxyimino]-3-methyl- pent-3-enic acid methyl ester
To 770 mg (1 .34 mmol) bis(dibenzylidenacetone)-palladium and 0.62 g (2.67 mmol) tri(2-fu- ryl)phosphine in 100 ml 1 ,4-dioxane 25.5 g (44.6 mmol) 1 -(2,4-dichloro-phenyl)-3-((Z)-3-tribu- tylstannanyl-but-2-enyloxy)-1 H-pyrazole and 9.17 g (46.8 mmol) hydroxamic acid bromide have been added with stirring. Stirring was continued for about 15 h at 84°C. After removal of the solvents in vacuo 80 ml MTBE and 80 ml of a 15% aqueous solution of potassium fluoride have been added and stirred for about 1 h at ambient temperature. After filtration the organic layer was collected. The aqueous phase was washed twice with 15 ml MTBE each. The combined organic phases have been dried with sodium sulphate. After filtration the solvents have been removed in vacuo to yield 14.0 g oil of sufficient purity (H-NMR) for the next reaction. P1.3 (Z)-5-[1 -(2,4-Dichloro-phenyl)-1 H-pyrazol-3-yloxy]-2-[(£)-methoxyimino]-3-methyl- pent-3- enic acid methyl amide
The product from several of the above reactions, which have partly been run on a larger scale, has been used in the following experiment. 930 g (2.34 mol) (Z)-5-[1 -(2, 4-dichloro-phe- nyl)-1 H-pyrazol-3-yloxy]-2-[(E)-methoxyimino]-3-methyl-pent-3-enic acid methyl ester have been dissolved in 5.0 I THF with stirring. 1226 g (15.8 mol) of a 40% solution of methyl amine in water have been added by pump within 1 min and stirred overnight at ambient temperature. After removal of most of the solvent in vacuo (at about 50°C, 75 mbar) the crude product was dissolved in 5.0 I of toluene at about 40°C with stirring for 30 min. The aqueous layer was removed at this temperature. 0.5 I of 15% aqueous sodium chloride solution were added and 1.5 I of aqueous layer could be removed afterwards. The toluene solution was washed with 2.0 I of 10% aqueous sodium chloride solution. The solvent was removed in vacuo (at about 60°C, 1 mbar). 860 g of crude product have been collected and stirred with 1.1 I of diisopropyl ether, filtrated and washed twice with 300 ml of cold diisopropyl ether each. The solvent has been removed in vacuo to yield 454 g of a finely crystalline solid. 1H-NMR (CDCI3): δ = 1.95 (s); 2.87 (d); 3.95 (s); 4.55 (d); 5.90 (d); 5.95 (t); 6.70 (broad); 7.30 (d); 7.45-7.55 (m); 7.70 (d), chemical purity determined via HPLC (wavelength 254 nm; column: Chromolith SpeedROD RP-18e 50-4.6 mm; gradient: 0.1 % trifluoroacetic acid; water : acetonitrile 1 :20 to 20 : 1 in 5.5 min): > 98 %. The PXRD pattern of the obtained mixture of crystalline form A and B, measured using Cu- Ka radiation at 25°C, is shown in Figure 1. By comparison with the peaks obtain for pure form crystalline form B (see Figure 2), it could be determined that a PXRD pattern of the crystalline form A shows at least the following peaks, given as 2Θ values: 6.8, 9.4 and 13.6.
The DSC curve measured using a 1 .6 mg sample by differential scanning calorimetry at a scan rate of 10°C per minute, exhibits a first endothermic peak with an onset temperature of about 107°C and a peak temperature of about 109°C, which is characteristic for crystalline form A. The second endothermic peak with an onset temperature of about 1 19°C and a peak temperature of about 123°C was found to belong to crystalline form B. Example P2: Preparation of crystalline form B of Compound I
P2.1 (Z,2£)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-/\/,3-dimethyl-pent-
3-enamide To 40.6 g (150 mmol) triphenylphosphine in 300 ml THF 31.3 g (150 mmol) azodicarbonic acid diisopropyl ester in 300 ml THF have been added dropwise with stirring at about -30°C. Stirring has been continued for 30 min at this temperature. Then 26.6 g (140 mmol) of compound 7 dissolved in 200 ml THF have been added dropwise with stirring at about -30°C. Stirring has been continued for 15 min at this temperature. 27.3 g (120 mmol) 1 -(2,4-dichloro- phenyl)-3-hydroxypyrazole dissolved in 1 .6 I of THF have been added dropwise with stirring at about -30°C. Stirring has been continued for 1 h at -30°C. The mixture was allowed to warm up to ambient temperature and stirred overnight. After removal of the solvents in vacuo the residue has been adsorbed on silica (200 g) and then purified by chromatography on silica (1 .6 kg column) with n-heptane/ethyl acetate. The crude product (54 g) was further purified by crystallisa- tion from 120 ml of boiling acetone which was cooled to 0°C. The resulting white crystals have been filtered off, washed with 40 ml of acetone/MTBE (1 :3) and dried in vacuo. Yield 31 .4 g of white crystals of crystalline form B of compound I. Purity by HPLC (see P1 .3): > 99 %.
The powder X-ray diffractogram of the obtained crystalline form B, measured using Cu-Ka radiation at 25°C, shows the following peaks, given as 2Θ values: 6.2°, 1 1.6°, 12.8°, 15.4°, 15.7°, 16.0°, 17.6°, 18.9°, 22.8°, 23.9°, 24.4°, 25.2°, 26.0° and 31.7° (see Figure 3).
The DSC curve measured using a 3.3 mg sample by differential scanning calorimetry at a scan rate of 10°C per minute, exhibits an endothermic peak with an onset temperature of about 123°C and peak temperature of about 125°C, which is characteristic for crystalline form B. The complete DSC curve is shown in Figure 4. The crystalline form B has been characterised further by single crystal X-ray diffratometry (SC-XRD) at a temperature of 100 K. It was found that the crystalline form is triclinic. The detailed unit cell parameters from the SC-XRD investigation using a single crystal diffracto meter from Bruker are shown in Table 1 .
Table 1 : Crystallographic data of crystalline form B.
Parameter single crystal data
Temperature 100 K
Chemical formula weight 397.25 g/mol
crystal system triclinic
space group ΡΪ
a 7.1874(3) A
b 9.031 1 (3) A
c 14.1827(5) A
a 89.761 (2)°
β 81.0440(10)°
Y 89.532(2)°
Volume 909.34(6) A3
Z 2
Density (calculated) 1 .451 g/cm3
The parameters shown have the following meaning:
a, b, c = edge lengths of the unit cell
α, β, Y = corresponding angles
Z = number of molecules in the nut cell
The atom positions for all atoms of the molecule of compound I relative to their position in the above-mentioned unit cell of crystalline form B have been determined from the SC-XRD data and are displayed in the Table 2.
Table 2: Atom positions within the unit cell of crystalline form B.
name atom X y z
CI01 CI 0.72534(13) 0.72626(1 1 ) -0.01259(7)
CI02 CI 0.73008(13) 0.13213(1 1 ) 0.02033(7)
01 0 0.8195(4) 0.0562(3) 0.44029(17)
02 0 0.2910(3) 0.2684(3) 0.57680(19)
03 0 0.7755(4) 0.4284(3) 0.7250(2)
N1 N 0.8600(4) 0.1931 (4) 0.21 19(2)
N2 N 0.7956(4) 0.2070(4) 0.3088(2)
N3 N 0.3842(4) 0.3861 (4) 0.61 12(2) name atom X y z
N4 N 0.5646(4) 0.5989(4) 0.6913(2)
H4 H 0.4641 0.6156 0.6669
C1 C 0.7712(5) 0.5671 (4) 0.0506(3)
C2 C 0.7413(5) 0.4301 (5) 0.0136(3)
H2 H 0.7009 0.4218 -0.0454
C3 C 0.7727(5) 0.3048(4) 0.0659(3)
C4 C 0.8355(5) 0.3176(5) 0.1536(3)
C5 c 0.8690(5) 0.4578(4) 0.1869(3)
H5 H 0.9141 0.4671 0.2446
C6 c 0.8368(5) 0.5828(5) 0.1365(3)
H6 H 0.8588 0.6762 0.1597
C7 C 0.9579(5) 0.0641 (4) 0.1937(3)
H7 H 1 .0161 0.0317 0.1341
C8 C 0.9560(5) -0.0087(5) 0.2769(3)
H8 H 1 .0098 -0.1004 0.2867
C9 C 0.8543(5) 0.0851 (4) 0.3458(3)
C10 C 0.6787(5) 0.1507(5) 0.4931 (3)
H10A H 0.5606 0.1420 0.4686
H10B H 0.7185 0.2531 0.4871
C1 1 C 0.6541 (5) 0.1033(5) 0.5954(3)
H1 1 H 0.6944 0.0084 0.6084
C12 C 0.5800(5) 0.1850(4) 0.6685(3)
C13 C 0.5481 (6) 0.1336(5) 0.7707(3)
H13A H 0.6179 0.0437 0.7763
H13B H 0.4163 0.1 158 0.7907
H13C H 0.5897 0.2084 0.8104
C14 C 0.5192(5) 0.3423(4) 0.6541 (3)
C15 C 0.6309(5) 0.4602(4) 0.6934(3)
C16 c 0.6579(6) 0.721 1 (5) 0.7292(3)
H16A H 0.7752 0.7401 0.6886
H16B H 0.6815 0.6968 0.7922
H16C H 0.5790 0.8078 0.7318
C17 C 0.1333(5) 0.3257(5) 0.5366(3)
H17A H 0.1763 0.3991 0.4892
H17B H 0.0440 0.3698 0.5861 name atom X y z
H17C H 0.0744 0.2465 0.5076
Brief description of the figures:
Figure 1. Powder X-ray diffractogram of a mixture of crystalline form A and B of compound I prepared according to Example P1. Peak positions marked with * are from form B (see Figure 4).
Figure 2. DSC curve of a mixture of crystalline form A and B of compound I prepared according to Example P1 (heating rate 10°C/min, exo up). Figure 3. Powder X-ray diffractogram of crystalline form B of compound I prepared according to Example P2.
Figure 4. DSC curve of crystalline form B of compound I prepared according to Example P2 (heating rate 10°C/min, exo up).
Figure 5. Asymmetric unit of crystalline form B of compound I (the numbering of the atoms is according to the nomenclature in Table 2).

Claims

Claims:
A crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino- A/,3-dimethyl-pent-3-enamide, which, in a powder X-ray diffractogram using Cu-KQ radiation at 25°C, shows at least the following three peaks, given as 2Θ values with an error margin of 0.2° 2Θ: 6.8°, 9.4° and 13.6°, or which, in a DSC curve measured by a differential scanning calorimeter at a scan rate of 10°C per minute, exhibits an endothermic peak with an onset temperature in the range of 95°C to 1 14°C.
The crystalline form according to claim 2, which, in a powder X-ray diffractogram using Cu-Κα radiation at 25°C, shows at least the following three peaks, given as 2Θ values with an error margin of 0.1 ° 2Θ: 6.8°, 9.4° and 13.6°, or which, in a DSC curve measured by a differential scanning calorimeter at a scan rate of 10°C per minute, exhibits an endothermic peak with an onset temperature in the range of 100°C to 1 10°C.
A crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino- N,3-dimethyl-pent-3-enamide, which, in a powder X-ray diffractogram using Cu-Κα radiation at 25°C, shows at least three of the six following peaks, given as 2Θ values with an error margin of 0.2° 2Θ: 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9°, or which, in a DSC curve measured by a differential scanning calorimeter at a scan rate of 10°C per minute, exhibits an endothermic peak with an onset temperature in the range of 1 15°C to 130°C.
The crystalline form according to claim 3, which, in a powder X-ray diffractogram using Cu-Κα radiation at 25°C, shows at least the following peaks, given as 2Θ values with an error margin of 0.2° 2Θ: 1 1.6°, 15.7°, and 18.9°.
The crystalline form according to any of the claims 3 to 4, which, in a powder X-ray diffractogram using Cu-Κα radiation at 25°C, shows at least five of the six following peaks, given as 2Θ values with an error margin of 0.2° 2Θ: 6.2°, 1 1 .6°, 15.7°, 17.6°, 18.9° and 23.9°, or which, in a DSC curve measured by a differential scanning calorimeter at a scan rate of 10°C per minute, exhibits an endothermic peak with an onset temperature in the range of 1 18°C to 128°C.
A mixture comprising as components
1 ) the crystalline form (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino- A/,3-dimethyl-pent-3-enamide as defined in any of the claims 1 to 2;
and
2) the crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino- A/,3-dimethyl-pent-3-enamide as defined in any of the claims 3 to 5. An agrochemical composition wherein said composition comprises an auxiliary and at least one crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxy- imino-A/,3-dimethyl-pent-3-enamide, as defined in any of the claims 1 to 5.
The composition according to claim 6 comprising at least one further active substance.
9. Use of at least one crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide as defined in any of the claims 1 to 5 for combating phytopathogenic fungi.
10. The use according to claim 9, wherein the phytopathogenic fungi contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, wherein the mutation is G143A. 1 1 . The use according to any of the claims 9 to 10, wherein the phytopathogenic fungi are selected from the group consisting of Alternaria alternata, Blumeria graminis, Magnaporthe grisea (anamorph: Pyricularia oryzae), Mycosphaerella graminicola (anamorph: Septoria tritici), Mycosphaerella fijiensis, Venturia inaequalis, Pyrenophora teres, Pyrenophona trit- ici-repentis (anamorph: Drechslera tritici-repentis) and Plasmopara viticola.
12. A method for combating phytopathogenic fungi as defined in any of the claims 9 to 1 1 , comprising:
treating the phytopathogenic fungi as defined in any of the claims 9 to 1 1 or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined in any of the claims 9 to 1 1 with an effective amount of at least one crystalline form of (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl- pent-3-enamide as defined in any of the claims 1 to 5, or a composition as defined in claims 7 to 8. 13. Plant propagation material, comprising at least one crystalline form of (Z,2E)-5-[1 -(2,4-di- chlorophenyl)pyrazol-3-yl]oxy-2 methoxyimino-A/,3-dimethyl-pent-3-enamide as defined in any of the claims 1 to 5 in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation material.
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