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WO2025120070A1 - Polymorphs of a methoxyacrylate derivative - Google Patents

Polymorphs of a methoxyacrylate derivative Download PDF

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Publication number
WO2025120070A1
WO2025120070A1 PCT/EP2024/084896 EP2024084896W WO2025120070A1 WO 2025120070 A1 WO2025120070 A1 WO 2025120070A1 EP 2024084896 W EP2024084896 W EP 2024084896W WO 2025120070 A1 WO2025120070 A1 WO 2025120070A1
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Prior art keywords
methyl
compound
prepared
methoxy
polymorph
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PCT/EP2024/084896
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French (fr)
Inventor
Adam KEATES
Yousif Khaled Mahyoub AL-SELWI
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Publication of WO2025120070A1 publication Critical patent/WO2025120070A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • 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
    • A01P3/00—Fungicides

Definitions

  • the present invention relates to solid forms of substituted meth oxacry late derivatives, compositions comprising the solid forms and methods of their use as fungicides.
  • W02020/193387, WO2021/176057 and W02022/200579 describe the use of methoxyacrylate derivatives for combating phytopathogenic fungi and methods for preparing said methoxyacrylate derivatives, in particular methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, shown below,
  • a novel crystalline polymorphic form of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate designated ‘form A’.
  • a crystalline polymorph, form A of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.0° ⁇ 0.2°, 18.6° ⁇ 0.2°, 20.3° ⁇ 0.2° and 22.0° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
  • a crystalline polymorph, form B of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.2° ⁇ 0.2°, 18.7° ⁇ 0.2°, 20.4° ⁇ 0.2° and 24.4° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
  • a novel crystalline polymorphic form of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate designated ‘form C’.
  • a crystalline polymorph form C of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.1 ° ⁇ 0.2°, 19.5° ⁇ 0.2°, 20.7° ⁇ 0.2° and 22.3° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .54184 A.
  • an agrochemical composition comprising a crystalline polymorph form A, or form B, or form C, of the compound methyl (Z)-2-(5-cyclohexyl-2- methyl-phenoxy)-3-methoxy-prop-2-enoate and an agrochemically acceptable carrier or diluent.
  • a method of controlling or preventing infestation by phytopathogenic fungi in a plant wherein a fungicidally effective amount of a crystalline polymorph form A, or form B, or form C, of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate, or a composition comprising said polymorph as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
  • a method of controlling or preventing infestation by phytopathogenic fungi in a plant wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qol inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a polymorph as described herein, or a composition comprising said polymorph as active ingredient.
  • the crystalline polymorph of the invention designated form A may be characterised by the unit cell parameters of its single crystal as shown below in Table 1. The polymorph was obtained using the method described in Example 1 .
  • the crystalline polymorph (form A) may also be characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles or d spacings.
  • the crystalline polymorph (form A) of the invention has a powder X-ray diffraction pattern comprising peaks at 12.0° ⁇ 0.2°, 18.6° ⁇ 0.2°, 20.3° ⁇ 0.2° and 22.0° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength (Cu Ka) of 1 .5406 A.
  • the polymorph further exhibits peaks at 16.5° ⁇ 0.2°, 18.2° ⁇ 0.2°, 23.5° ⁇ 0.2°, 24.7° ⁇ 0.2° and 26.6° ⁇ 0.2° 20. More preferably, the polymorph further exhibits peaks at 14.9° ⁇ 0.2°, 16.9° ⁇ 0.2°, 17.7° ⁇ 0.2°, 21.5° ⁇ 0.2°, 21.8° ⁇ 0.2°, 24.5° ⁇ 0.2° and 27.4° ⁇ 0.2° 20.
  • the crystalline polymorph (form A) of the invention has a powder X-ray diffraction pattern comprising peaks at 12.0° ⁇ 0.2°, 16.5° ⁇ 0.2°, 18.2° ⁇ 0.2°, 18.6° ⁇ 0.2°, 20.3° ⁇ 0.2°, 22.0° ⁇ 0.2°, 23.5° ⁇ 0.2°, 24.7° ⁇ 0.2° and 26.6° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
  • the crystalline polymorph (form A) of the invention has a powder X-ray diffraction pattern comprising peaks at 12.0° ⁇ 0.2°, 14.9° ⁇ 0.2°, 16.5° ⁇ 0.2°, 16.9° ⁇ 0.2°, 17.7° ⁇ 0.2°, 18.2° ⁇ 0.2°, 18.6° ⁇ 0.2°, 20.3° ⁇ 0.2°, 21.5° ⁇ 0.2°, 21.8° ⁇ 0.2°, 22.0° ⁇ 0.2°, 23.5° ⁇ 0.2°, 24.5° ⁇ 0.2°, 24.7° ⁇ 0.2°, 26.6° ⁇ 0.2° and 27.4° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
  • the crystalline polymorph (form A) of the invention has a powder X-ray diffraction pattern comprising the peaks substantially as shown in figure 1 and listed in table 2 below (along with the corresponding d spacing and relative intensity values):
  • a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate wherein the polymorph has a melting point of from 101 °C to 107 °C (preferably, from 101 °C to 106 °C, more preferably, 102 °C to 106 °C and even more preferably, 102 °C to 105 °C).
  • This melting point is obtained using Differential Scanning Calorimetry (DSC) with a heating rate of 10 °C/minute.
  • a further crystalline polymorph, of the invention designated form B may be obtained using the method described in Example 2.
  • the crystalline polymorph (form B) may also be characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles or d spacings.
  • a crystalline polymorph form B of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.2° ⁇ 0.2°, 18.7° ⁇ 0.2°, 20.4° ⁇ 0.2° and 24.4° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
  • the polymorph further exhibits peaks at 8.4° ⁇ 0.2°, 10.2° ⁇ 0.2°, 18.5° ⁇ 0.2°, 22.1 ° ⁇ 0.2°, 22.9° ⁇ 0.2°, 23.7° ⁇ 0.2° and 24.9° ⁇ 0.2° 20. More preferably, the polymorph further exhibits peaks at 15.9° ⁇ 0.2°, 17.4° ⁇ 0.2°, 18.2° ⁇ 0.2°, 23.3° ⁇ 0.2° and 27.6° ⁇ 0.2° 20.
  • the crystalline polymorph (form B) of the invention has a powder X-ray diffraction pattern comprising peaks at 8.4° ⁇ 0.2°, 10.2° ⁇ 0.2°, 12.2° ⁇ 0.2°, 18.5° ⁇ 0.2°, 18.7° ⁇ 0.2°, 20.4° ⁇ 0.2°, 22.1 ° ⁇ 0.2°, 22.9° ⁇ 0.2°, 23.7° ⁇ 0.2°, 24.4° ⁇ 0.2° and 24.9° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
  • the crystalline polymorph (form B) of the invention has a powder X-ray diffraction pattern comprising peaks at 8.4° ⁇ 0.2°, 10.2° ⁇ 0.2°, 12.2° ⁇ 0.2°, 15.9° ⁇ 0.2°, 17.4° ⁇ 0.2°, 18.2° ⁇ 0.2°, 18.5° ⁇ 0.2°, 18.7° ⁇ 0.2°, 20.4° ⁇ 0.2°, 22.1 ° ⁇ 0.2°, 22.9° ⁇ 0.2°, 23.3° ⁇ 0.2°, 23.7° ⁇ 0.2°, 24.4° ⁇ 0.2°, 24.9° ⁇ 0.2° and and 27.6° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
  • the crystalline polymorph (form B) of the invention has a powder X-ray diffraction pattern comprising the peaks substantially as shown in figure 2 and listed in table 3 below (along with the corresponding d spacing and relative intensity values):
  • a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate wherein the polymorph has a melting point of from 94 °C to 98 °C (preferably, from 95 °C to 97 °C). This melting point is obtained using Differential Scanning Calorimetry (DSC) with a heating rate of 10 °C/minute.
  • DSC Differential Scanning Calorimetry
  • a further crystalline polymorph, of the invention designated form C may obtained using the method described in Example 3.
  • the crystalline polymorph (form C) may also be characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles or d spacings.
  • a crystalline polymorph form C of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.1 ° ⁇ 0.2°, 19.5° ⁇ 0.2°, 20.7° ⁇ 0.2° and 22.3° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1.54184 A.
  • the polymorph further exhibits peaks at at 8.9° ⁇ 0.2°, 16.4° ⁇ 0.2°, 17.6° ⁇ 0.2°, 18.1 ° ⁇ 0.2°, 21.4° ⁇ 0.2°, 24.9° ⁇ 0.2° and 25.0° ⁇ 0.2° 20. More preferably, the polymorph further exhibits peaks at 15.7° ⁇ 0.2°, 24.3° ⁇ 0.2°, 26.5° ⁇ 0.2°, 27.6° ⁇ 0.2°, 28.1 ° ⁇ 0.2° 20 and 28.6° ⁇ 0.2° 20.
  • the crystalline polymorph (form C) of the invention has a powder X-ray diffraction pattern comprising peaks at 8.9° ⁇ 0.2°, 12.1 ° ⁇ 0.2°, 16.4° ⁇ 0.2°, 17.6° ⁇ 0.2°, 18.1 ° ⁇ 0.2°, 19.5° ⁇ 0.2°, 20.7° ⁇ 0.2°, 21.4° ⁇ 0.2°, 22.3° ⁇ 0.2° 20, 24.9° ⁇ 0.2° and 25.0° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .54184 A.
  • the crystalline polymorph (form C) of the invention has a powder X-ray diffraction pattern comprising peaks at 8.9° ⁇ 0.2°, 12.1 ° ⁇ 0.2°, 15.7° ⁇ 0.2°, 16.4° ⁇ 0.2°, 17.6° ⁇ 0.2°, 18.1 ° ⁇ 0.2°, 19.5° ⁇ 0.2°, 20.7° ⁇ 0.2°, 21.4° ⁇ 0.2°, 22.3° ⁇ 0.2° 20, 24.3° ⁇ 0.2°, 24.9° ⁇ 0.2°, 25.0° ⁇ 0.2°, 26.5° ⁇ 0.2°, 27.6° ⁇ 0.2°, 28.1 ° ⁇ 0.2° 20 and 28.6° ⁇ 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .54184 A.
  • the crystalline polymorph (form C) of the invention has a powder X-ray diffraction pattern comprising the peaks substantially as shown in figure 3 and listed in table 4 below (along with the corresponding d spacing and relative intensity values):
  • the crystalline polymorph of the invention designated form C may also be characterised by the unit cell parameters of its single crystal as shown below in Table 5. The polymorph was obtained using the method described in Example 1 .
  • Tm melting point (K) (obtained from DSC data)
  • form A and form B it can be seen from the solubility vs. temperature plot (Fig 6) that form A is the monotropic stable polymorph compared to form B.
  • form A is the monotropic stable polymorph compared to form B.
  • a polymorph is a particular crystal form of a chemical compound that can exist in more than one crystal form in the solid state.
  • a crystal form of a compound contains the consitituent molecules arranged in orderly repeating patterns extending in all three spatial dimensions (in contrast, an amorphous solid form has no long-range order in the position of molecules).
  • Different polymorphs of a compound have different arrangements of atoms and or molecules in their crystal structure.
  • the compound is a biologically active compound, such as a fungicide
  • the difference in crystal structures can lead to different polymorphs having differing chemical, physical and biological properties. Properties which may be affected include crystal shape, density, hardness, colour, chemical stability, melting point, hydroscopicity, suspensibility, dissolution rate and biological availability.
  • a specific polymorph may have properties which make it more advantageous in a particular use relative to another polymorph of the same compound: in particular, the physical, chemical and biological properties listed above and have a significant effect on the development of production methods and formulations, the ease with which a compound can be combined in a formulation with other active ingredients and formuation components and the quality and efficacy of plant treatment agents, such as fungicides. It is noted that predicting whether the solid state of a compound may be present as more than one polymorph is not possible and nor is it possible to predict the properties of any of these crystal forms.
  • a specific polymorph may allow the use of new formulations compared with existing polymorphic/amorphous forms of a compound.
  • SC suspension concentrate
  • EC emulsion concentrate
  • the lack of solvent in the SC often means that the formulation is likely to be less phytotoxic than an equivalent EC formulation - however, if the existing form of a compound is not stable in such an SC formulations, polymorphic conversion might occur leading to unwanted crystal growth.
  • Such crystal growth is detrimental because it leads to, for example, thickening and potentially solidification of the formulation which can lead to blockages in application equipment, e.g in spray nozzles in agricultural application machinery.
  • Using a stable polymorphic form would overcome these issues.
  • Assaying the solid phase for the presence of crystals may be carried out be conventional methods known in the art. For example, it is convenient and routine to use powder X-ray diffraction techniques. Othertechniques which may be used include differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and Raman or Infra-red spectroscopy, NMR, gas chromatography or HPLC. Single crystal X-ray diffraction is especially useful in identifying crystal structures.
  • the polymorph of the invention may be applied in unchanged form but is more preferably incorporated into agrochemical compositions by conventional means. Accordingly, in a further aspect, the invention provides an agrochemical composition comprising the polymorph of the invention as defined above and at least one agriculturally acceptable carrier or diluent.
  • an agrochemical composition comprising a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein and an agrochemically acceptable carrier or diluent.
  • an agrochemical composition comprising a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein and an agrochemically acceptable carrier or diluent.
  • an agrochemical composition comprising a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein and an agrochemically acceptable carrier or diluent.
  • a method of controlling or preventing infestation by phytopathogenic fungi in a plant wherein a fungicidally effective amount of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, or a composition comprising said polymorph as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
  • a method of controlling or preventing infestation by phytopathogenic fungi in a plant wherein a fungicidally effective amount of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, or a composition comprising said polymorph as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
  • a method of controlling or preventing infestation by phytopathogenic fungi in a plant wherein a fungicidally effective amount of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, or a composition comprising said polymorph as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
  • a method of controlling or preventing infestation by phytopathogenic fungi in a plant wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qol inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidally effective amount of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, or a composition comprising said polymorph as active ingredient.
  • a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein
  • a method of controlling or preventing infestation by phytopathogenic fungi in a plant wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qol inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidally effective amount of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate as defined herein, or a composition comprising said polymorph as active ingredient.
  • a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate as defined herein
  • a method of controlling or preventing infestation by phytopathogenic fungi in a plant wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qol inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidally effective amount of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate as defined herein, or a composition comprising said polymorph as active ingredient.
  • polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate according to the invention can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man.
  • the novel polymorphs are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants.
  • the polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
  • the present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein a fungicidally effective amount of a crystalline polymorph form A, or form B, or form C of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate is applied to the plants, to parts thereof or the locus thereof.
  • the present invention relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein a fungicidally effective amount of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to the plants, to parts thereof or the locus thereof.
  • a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to the plants, to parts thereof or the locus thereof.
  • the present invention relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein a fungicidally effective amount of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to the plants, to parts thereof or the locus thereof.
  • a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to the plants, to parts thereof or the locus thereof.
  • the present invention relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein a fungicidally effective amount of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to the plants, to parts thereof or the locus thereof.
  • a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to the plants, to parts thereof or the locus thereof.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • fungicidally effective amount means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants.
  • locus means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • polymorphs (form A, orform B, orform C) of the compound methyl (Z)-2-(5-cyclohexyl- 2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
  • the invention could be used to protect non-living materials from fungal attack, e.g., lumber, wall boards and paint.
  • polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
  • polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein and/or agrochemical compositions comprising the polymorph of the present invention are effective in controlling a broad spectrum of plant diseases, such as foliar and/or soil-borne pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.
  • pathogens may include:
  • Oomycetes including Phytophthora species such as Phytophthora cactorum, Phytophthora capsici, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, Phytophthora erythrose ptica, Phytophthora fragariae, Phytophthora infestans, Phytophthora nicotianae, Phytophthora porri, and Phytophthora sojae; Pythium species such as Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; other Peronosporales such as Bremia lactucae, Hyaloperonospora parasitica, Hyaloperonospora brassicae, Sclerophthora macrospora, Sclerospora graminicola Peronospora species including Per
  • Plasmopara species including Plasmopara halstedii and Plasmopara viticola; Pseudoperonospora species including Pseudoperonospora cubensis and Pseudoperonospora humili; Peronosclerospora species including Peronosclerospora maydis, Peronosclerospora philippinensis and Peronosclerospora sorghi; Albuginales such as Albugo Candida, Albugo occidentalis, and Albugo tragopogonis; and Saprolegniales such as Aphanomyces species, including Aphanomyces cochliodes.
  • Ascomycetes including Mycosphaerellales such as Actinothyrium graminis, Asperisporium caricae, Cercospora species including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf.
  • Neocosmospora phaseoli Neocosmospora solani, Neonectria Candida, Paramyrothecium roridum, Sarocladium oryzae, Trichoderma species including Trichoderma harzianum, Trichoderma pseudokoningii and Trichoderma viride; Trichothecium roseum and Ustilaginoidea virens; Magnaporthales such as Gaeumannomyces avenae, Gaeumannomyces graminis, Gaeumannomyces graminis tritici, Gaeumannomyces wongoonoo, Magnaporthiopsis poae, Pyricularia species including Pyricularia gris
  • Botryosphaeriales such as Botryosphaeria species including Botryosphaeria dothidea; Diplodia species including Diplodia seriata; Dothiorella aromatica, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta ampelicida and Phyllosticta cucurbitacearum; Eurotiales such as Aspergillus species including Aspergillus flavus, Aspergillus fumigatus, Aspergillus niger and Aspergillus terreus; Penicillium species including Penicillium digitatum, Penicillium expansum and Penicillium italicum; Microascales such as Berkeleyomyces basicola, Thielaviopsis paradoxa, Ceratocystis species including Ceratocystis fimbriata, Ceratocystis manginecans and Ceratocystis
  • Sordariomycetes such as Wongia garrettii and Wongia griffinii
  • Taphrinales such as Taphrina bullata and Taphrina deformans
  • Onygenales such as Ajellomyces capsulatus, Blastomyces dermatitidis, Coccidioides species including Coccidioides immitis
  • Epidermophyton spp. Histoplasma spp.
  • Microsporum spp. Trichophyton spp.
  • Paracoccidioides species including Paracoccioides brasiliensis
  • others such as Hymenula cerealis, Petriellidum spp., and Septocyta ruborum.
  • Basidiomycetes including Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Cron art! urn ribicola, Gymnosporangium juniperi-virginianae, Gymnosporangium sabinae, Hemileia species including Hemileia vastatrix; Melampsora medusae, Melampsora lini, Phakopsora ampelopsidis, Phakopsora pachyrhizi, Phragmidium mucronatum, Puccinia species including Puccinia aim, Puccinia arachidis, Puccinia asparagi, Puccinia cacabata, Puccinia coronata, Puccinia graminis, Puccinia helianthi, Puccinia hieracii, Puccinia horde!
  • Pucciniales such as Cerotelium fici
  • Puccinia horiana Puccinia melanocephala, Puccinia polysora, Puccinia porri, Puccinia recondita, Puccinia sorghi, Puccinia striiformis, Puccinia striiformis f.sp. horde!, Puccinia striiformis f.sp. tritici and Puccinia triticina; Pucciniastrum coryli, Tranzschelia discolor, Uromyces species including Uromyces betae, Uromyces pis!
  • Tilletiales such as Neovossia moliniae, and Tilletia species including Tilletia caries and Tilletia controversa
  • Ustilaginales such as Sporisorium reilianum and Ustilago species including Ustilago maydis, Ustilago segetum var. nuda, Ustilago segetum var.
  • Urocystidales such as Urocystis species including Urocystis agropyri
  • Agaricales such as Marasmiellus inoderma, Mycena spp., Moniliophthora roreri and Moniliophthora perniciosa
  • Cantharellales such as Sclerotium spp. and Typhula species including Typhula incarnata and Typhula ishikariensis
  • Ceratobasidiales such as Waitea circinata, and Rhizoctonia species including Rhizoctonia cerealis, Rhizoctonia solan!
  • Atheliales such as Athelia rolfsii; Corticiales such as Corticium invisum and Laetisaria fuciformis; Cystodilobasidiales such as Itersonilia perplexans; Entylomatales such as Entyloma calendulae f.sp. dahliae and Entylomella microspore; Exobasidiales such as Exobasidium vexans; Hymenochaetales such as Phellinus igniarius; Russulales such as Stereum hirsutum; and Tremellales such as Cryptococcus species including Cryptococcus neoformans.
  • Mucorales such as Choanephora cucurbitarum, Mucor spp., Rhizopus oryzae, Absidia corymbifera and Rhizomucor pusillus.
  • compositions may also have activity against diseases caused by Actinobacteria such as Streptomyces scabiei; Proteobacteria such as Erwinia amylovora, Pectobacterium carotovorum, Xanthomonas species including Xanthomonas axonopodis, Xanthomonas campestris, Xanthomonas citri, Xanthomonas oryzae and Xanthomonas vesicatoria Xylella fastidiosa, and Pseudomonas species including Pseudomonas syringae Cercozoa such as Polymyxa betae, Polymyxa graminis and Spongospora subterranea; and Bigyra such as Labyrinthula zosterae. as well as diseases caused by other species and genera closely related to those listed above.
  • Actinobacteria such as Streptomyces s
  • the polymorphs of the present invention as disclosed herein are particularly effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (also known as Deuteromycetes; e.g.
  • Ascomycetes e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula
  • Basidiomycetes e.g. the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia
  • Fungi imperfecti also known as Deuteromycetes
  • Botrytis Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella); Oomycetes (e.g. Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara).
  • the polymorphs (form A, or form B, or form C) of the compound methyl (Z)- 2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), can be used on the following crops and pathogens:
  • the polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl- 2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), are suitable for controlling the following fungal diseases on soybeans and genetically modified soybeans, for example Bt soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (Cercospora leaf spots), e.g., C. sojina or C. kikuchii Colletotrichum (teleomorph: Glomerella) spp. (anthracnose), e.g., C. truncatum or C.
  • gloeosporioides Corynespora cassiicola (leaf spots); Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot); Diaporthe spp., e.g., D. phaseolorum (damping off); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot), e.g. F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans; Macrophomina phaseolina (syn. phaseoli) (root and stem rot); Microsphaera diffusa (powdery mildew); Peronospora spp.
  • Rhizoctonia spp. e.g., R. solani (root and stem rot); Sclerotinia spp. (stem rot or white mold); Septoria spp., e.g., S. glycines (brown spot); S. rolfsii (syn. Athelia rolfsii); Thielaviopsis spp. (black root rot).
  • the polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), are suitable for controlling the following fungal diseases on soybeans and genetically modified soybeans, for example Bt soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (Cercospora leaf spots), e.g., C. sojina or C. kikuchii); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose), e.g., C.
  • Phomopsis spp. e.g., stem rot: P. phaseoli (teleomorph: Diaporthe phaseolorum); Phytophthora spp. (wilt, root, leaf, fruit and stem root), e.g., P. megasperma, syn. P. sojae); Rhizoctonia spp., e.g., R. solani (root and stem rot); Septoria spp., e.g., S. glycines (brown spot).
  • stem rot P. phaseoli (teleomorph: Diaporthe phaseolorum)
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • Rhizoctonia spp. e.g., R. solani (root and stem rot)
  • Septoria spp. e.g., S. glycines (brown spot).
  • polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), according to the present invention are particularly important for controlling phyto- pathogenic harmful fungi on soybeans and genetically modified soybeans, for example Bt soybeans.
  • polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), according to the present invention are also particularly important for controlling Phakopsora pachyrhizi, P.
  • soybeans and genetically modified soybeans for example Bt soybeans.
  • Crops of useful plants in which the compositions comprising the polymorph of the present invention disclosed herein can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
  • perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
  • cereals for example bar
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
  • legumes for example beans, lentils, peas and soya beans
  • useful plants is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a Cryll IB(b1 ) toxin); Starlink* (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N- acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety
  • Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors.
  • herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors.
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola.
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
  • Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include 8- endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.
  • Vip vegetative insecticidal proteins
  • insecticidal proteins of bacteria colonising nematodes and toxins produced by scorpions, arachnids, wasps and fungi.
  • An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds).
  • An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds).
  • Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification).
  • a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
  • the fungicidal compositions comprising the polymorphs as disclosed herein as active ingredients, may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on transgenic soybean plants.
  • phytopathogenic diseases especially phytopathogenic fungi (such as Phakopsora pachyrhizi)
  • transgenic soybean plants expressing toxins, for example insecticidal proteins such as delta-endotoxins, e.g. CrylAc (CrylAc Bt protein).
  • this may include transgenic soybean plants comprising event MON87701 (disclosed in W02009/064652, as well as WO2014/170327 (eg, see paragraph [008] reference to Intacta RR2 PRO® soybean)), event MON87751 (disclosed in WO2014/201235) or event DAS-81419-2 (aka ConkestaTM Soybean, described in WO2013016527).
  • transgenic events in transgenic soybean plants include event DAS-44406-6/pDAB8264.44.06.1 (soybean, herbicide-tolerance, disclosed in WO2012/075426); event DAS-81419-2 (aka ConkestaTM Soybean, described in WO2013016527 (aka ConkestaTM Enlist E3TM Soybean, DAS-81419-2 x DAS-44406-6); event DAS-14536- 7/pDAB8291 .45.36.2 (soybean, herbicide-tolerance, disclosed in WO2012/075429); DAS-68416-4 (soybean, herbicide-tolerance, ATCC Accession No.
  • PTA-10442 disclosed in WO201 1/066384, WO201 1/066360
  • event DP-305423-1 (soybean, quality mark, disclosed in W02008/054747); event DP-356043-5 (soybean, herbicide-tolerance, deposited as ATCC PTA-8287, disclosed in W02008/002872); event FG72 (soybean, herbicide-tolerance, disclosed in WO201 1/063413); event LL27 (soybean, herbicide-tolerance, disclosed in W02006/108674); event LL55 (soybean, herbicidetolerance, disclosed in WO 2006/108675); event EE-GM3/FG72 (soybean, herbicide-tolerance) optionally stacked with event EE-GM1/LL27 or event EE-GM2/LL55 (disclosed in WO201 1/063413); event MON87701 (soybean, insect control, disclosed in W0
  • transgenic events in transgenic soybean plants include event A2704-12 (glufosinate tolerance, disclosed in W02006/108647), event A5547-127 (phosphinothricin tolerant, disclosed in W02006/108675); event GU262 (phosphinothricin tolerant, described in APHIS regulatory reference US 98-238-01 p); event MON89788 (disclosed in W02006/130494A; event DP-305423-1 (soybean, quality mark, disclosed in W02008/054747); event MON87701 (soybean, insect resistant, disclosed in W02009/064652); event MON87705 (soybean, improved fatty acid profile, herbicide-tolerance, disclosed in WO2010/037016 or US20100080887A); event MON87769 (soybean, quality attribute, disclosed in W02009/102873 or US20110067141A); event FG72 (s
  • event DAS-68416-4 (soybean, herbicide-tolerance, ATCC Accession No. PTA-10442, disclosed in WO2011/066384, WO2011/066360); event SYHT0H2/SYN-000H2-5 (soybean, herbicide-tolerance, disclosed in WO2012/082548); event DAS-44406-6/pDAB8264.44.06.1 (soybean, herbicide-tolerance, disclosed in WO2012/075426); event MON87751 (lepidopteran-resistant, ATCC accession no. PTA- 120166.
  • event MON87708 (soybean, herbicide-tolerance, disclosed in WO2011/034704)
  • event GMB151 also called BCS-GM151-6, HPPD tolerance, disclosed in WO2018119364A1.
  • transgenic events are provided by the United States Department of Agriculture's (USDA) Animal and Plant Health Inspection Service (APHIS) and can be found on their website on the World Wide Web at aphis.usda.gov.
  • USDA United States Department of Agriculture's
  • APIS Animal and Plant Health Inspection Service
  • event refers to the event name that relates to a unique DNA recombination event that took place in one plant cell and which was then used to generate an entire transgenic plant. Detailed information on the events and associated products can be found on http://www.isaaa.org/gmapprovaldatabase. The events listed herein have been introduced into plants that are now commercially available.
  • transgenic soybeans which can preferably be treated in a method according to the invention, include commercially available products such as plant seeds, which are under the ROUNDUP READY 2 XTEN®, INTACTA RR2 PRO®, VISTIVE® GOLD, Conkesta E3®, Conkesta Enlist E3TM, LibertyLink® and/or Xtend Flex® trade names are sold or distributed.
  • Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704- 21 , A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
  • Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21
  • Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21
  • Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21
  • the fungicidal polymorphs and compositions as disclosed herein may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soybean plants.
  • phytopathogenic diseases especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soybean plants.
  • phytopathogenic fungi such as Phakopsora pachyrhizi
  • An elite plant is any plant from an elite line, such that an elite plant is a representative plant from an elite variety.
  • elite soybean varieties that are commercially available to farmers or soybean breeders include: AG00802, A0868, AG0902, A1923, AG2403, A2824, A3704, A4324, A5404, AG5903, AG6202 AG0934; AG1435; AG2031 ; AG2035; AG2433; AG2733; AG2933; AG3334; AG3832; AG4135; AG4632; AG4934; AG5831 ; AG6534; and AG7231 (Asgrow Seeds, Des Moines, Iowa, USA); BPR0144RR, BPR 4077NRR and BPR 4390NRR (Bio Plant Research, Camp Point, III., USA); DKB17- 51 and DKB37-51 (DeKalb Genetics, DeKalb, III., USA); DP 4546 RR, and DP 7870 RR (Delta & Pine Land Company, Lubbock,
  • fungicidal polymorphs and compositions as disclosed herein are used to control Phakopsora pachyrhizi, (including fungicidally-resistant strains thereof, as outlined below) on Elite soybean plant varieties where R-gene stacks, conferring a degree of immunity or resistance to specific Phakopsora pachyrhizi, have been been introgressed in the plant genome.
  • Numerous benefits may be expected to ensue from said use, e.g. improved biological activity, an advantageous or broader spectrum of activity (inc.
  • Phakopsora pachyrhizi sensitive and resistant strains of Phakopsora pachyrhizi
  • an increased safety profile improved crop tolerance, synergistic interactions or potentiating properties, improved onset of action or a longer lasting residual activity, a reduction in the number of applications and/or a reduction in the application rate of the compounds and compositions required for effective control of the phytopathogen (Phakopsora pachyrhizi), thereby enabling beneficial resistancemanagement practices, reduced environmental impact and reduced operator exposure.
  • fungicidal compositions comprising the polymorphs according to the present invention and at least one additional active ingredient, when used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants (in particular any of the transgenic soybean plants as described above), may display a synergistic interaction between the active ingredients.
  • Exemplary GM traits that confer enhanced ASR resistance comprise resistance genes encoding resistance proteins as set forth in: W02019103918 (for example, but not limited to, RG-1 (SEQ ID NO: 47) and active variants or fragments thereof; or R-genes as set forth at SEQ ID NO: 28, 42, 43, 44, 45 or 46 ofW02019103918); WO202100878 (for example Rpp6907 (SEQ ID NO: 1 of WO202100878) and active variants or fragments thereof); WO2021022022 (for example, TirA or Tir B (SEQ ID NOS: 11 or 16 of WO2021022022, respectively) or active variants or fragments thereof); WO2021260673 (for example, but not limited to, RG21 and/or RG22 (SEQ ID NOS: 1 or 12 of WO2021260673) or active variants or fragments thereof); WO2022173659 (for example, but not limited to, RG30 (SEQ ID NO: 5 of WO20
  • RG35 SEQ ID NOS: 2 or 5
  • Exemplary native traits that confer increased resistance to ASR or to pathogens from the genus Phakopsora include various intervals and locus (loci) associated with Rpp1 , Rppl b, Rpp2, Rpp4, Rpp5, Rpp6 and ASR resistance locus 1-16.
  • Such native traits can be found, for example, in W02009079729, US8759607, US8962914, W02008054546, US8692054, US9091681 , W02009132089, US8669414, US8796503, US8921645, WO2010096227, WO2010009404, WQ2021154632, US20230067451 , WQ2021022026, US20220256795, WQ2021022101 , US20220338433A1 , WQ2022173659, WQ2010009404, WQ2017222827, US20210024950, WQ2021000878, US20220380796, US20230147114, and PCT App. No. PCT/US23/60373, each of which is incorporated by reference in their entirety.
  • Exemplary Soybean varieties that confer increased resistance to ASR include soybean cultivars TMG 7062, TMG 7161 and TMG 7261 .
  • Soybean varieties that confer increased resistance against ASR (caused by Phakopsora pachyrhizi) inlcude for example, but not limited to TMG7368 IPRO (Disclosed in WQ2009079729), TMG7062 IPRO, TMG 7063 IPRO, and TMG 7061 IPRO.
  • Further Soybean varieties that confer increased resistance against ASR (caused by Phakopsora pachyrhizi) inlcude for example, but not limited to soybeans with Shield Technology, like for example BRS511 soybean, BRS 531 soybean, or Soy-BRS 539 (conventional soybean with Shield® and Block® Technologies).
  • Fungicidal-resistant strains of Phakopsora pachyrhizi have been reported in the scientific literature, with strains resistant to one or more fungicides from at least each of the following fungicidal mode of action classes being observed: sterol demethylation-inhibitors (DMI), quinone-outside-inhibitors (Qol) and succinate dehydrogenase inhibitors (SDHI).
  • DMI sterol demethylation-inhibitors
  • Qol quinone-outside-inhibitors
  • SDHI succinate dehydrogenase inhibitors
  • the genetically modified plants are soybean plants.
  • Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), lntacta®2 XtendTM, Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Roundup ReadyTM 2 XtendTM, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, PlenishTM.
  • the genetically modified plants are Bt soybean plants.
  • “Bt plants” are for example soybean varieties which are sold under the trade names Intacta®, lntacta®2, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, PlenishTM. Even more preferably, the Bt soybean plants are selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
  • the genetically modified plants are soybean plants.
  • Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), lntacta®2 XtendTM, Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Roundup ReadyTM 2 XtendTM, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, PlenishTM.
  • the genetically modified plants are Bt soybean plants.
  • “Bt plants” are for example soybean varieties which are sold under the trade names Intacta®, lntacta®2, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, PlenishTM. Even more preferably, the Bt soybean plants are selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
  • the genetically modified plants are soybean plants.
  • Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), lntacta®2 XtendTM, Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Roundup ReadyTM 2 XtendTM, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, PlenishTM.
  • the genetically modified plants are Bt soybean plants.
  • “Bt plants” are for example soybean varieties which are sold under the trade names Intacta®, lntacta®2, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, PlenishTM. Even more preferably, the Bt soybean plants are selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
  • soybean plants are Bt soybean plants, preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®, characterized by comprising the step of contacting the plant, parts thereof, propagation material thereof, the pests, their food source, habitat, or breeding ground with a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate.
  • soybean plants are Bt soybean plants, preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®, characterized by comprising the step of contacting the plant, parts thereof, propagation material thereof, the pests, their food source, habitat, or breeding ground with a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2- methyl-phenoxy)-3-methoxy-prop-2-enoate.
  • soybean plants are Bt soybean plants, preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®, characterized by comprising the step of contacting the plant, parts thereof, propagation material thereof, the pests, their food source, habitat, or breeding ground with a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2- methyl-phenoxy)-3-methoxy-prop-2-enoate.
  • genetically modified soybean plants which can preferably be treated according to the invention, include commercially available products such as plant seeds, which are under the Intacta®, lntacta®2, lntacta®2 XtendTM, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Roundup ReadyTM 2 XtendTM, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, or PlenishTM trade names are sold or distributed.
  • Bt soybean plants which can preferably be treated according to the invention, include commercially available products such as plant seeds, which are sold under the trade names Intacta®, lntacta®2, lntacta®2 XtendTM, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Roundup ReadyTM 2 XtendTM, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, or PlenishTM.
  • genetically modified soybean plants which can be treated according to the invention, are selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
  • the genetically modified plants are soybean plants. More preferably said genetically modified soybean plants are Bt soybean plants, even more preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
  • the genetically modified plants are soybean plants. More preferably said genetically modified soybean plants are Bt soybean plants, even more preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
  • the genetically modified plants are soybean plants. More preferably said genetically modified soybean plants are Bt soybean plants, even more preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
  • genetically modified plant or “genetically modified soybean plant” refers to a plant or soybean plant, in which the genetic material has been altered in a way that does not occur naturally by mating and /or natural recombination. These plants are also called transgenic or genetically engineered plants. Genetic modification of plants involves adding a specific stretch of DNA into the plant’s genome, giving it new or different characteristics. This could include changing the way the plant grows or making it resistant to a particular disease.
  • Examples of genetically modified soybean plants are available under the tradenames YIELD GARD®, Intacta®, lntacta®2, Intacta® Roundup ReadyTM 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3TM Soybean, EnlistTM Soybean, Enlist E3TM Soybean, Roundup ReadyTM Soybean, Genuity® Roundup ReadyTM 2 XtendTM, Genuity® Roundup Ready 2 YieldTM, Herbicide-tolerant Soybean line, Optimum GATTM, Liberty LinkTM Soybean, Vistive GoldTM, Verdeca HB4 Soybean, TreusTM, PlenishTM.
  • Bt soybean plant refers to soybean plants that are genetically engineered soybeans that produce an insecticidal protein like the one naturally produced by the bacteria species Bacillus thuringiensis, for example by the genes CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, Cry II IB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and also combinations thereof.
  • Bt soybeans soybeans that are genetically engineered to produce the same toxin as Bacillus thuringiensis (Bt) in every cell of the plant, with the goal of protecting the soybean from pests.
  • Bt soybean plants are Intacta RR2 PRO®, or Conkesta Enlist E3®.
  • the polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g., in polymeric substances.
  • compositions As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating, or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. e.g., natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
  • substances useful in formulation technology e.g. e.g., natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
  • Such carriers are for example described in WO 1997/33890.
  • Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
  • the particles contain the active ingredient retained in a solid matrix.
  • Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required.
  • Typical carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours, and other organic and inorganic solids which act as dispersants and carriers.
  • the active ingredients can also be contained in micro-'capsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g., slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane, or chemically modified polymers, and starch xanthates, or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates.
  • Encapsulated droplets are typically 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurised sprayers wherein the active ingredient is dispersed in finely divided form as a result ofbecause of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to a person skilled in the art.
  • Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol di
  • Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application.
  • These agents when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
  • Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.
  • alcohol-alkylene oxide addition products such as tridecyl alcohol-C.sub. 16 ethoxylate
  • soaps such as sodium stearate
  • alkylnaphthalenesulfonate salts such as sodium dibutylnaphthalenesulfonate
  • dialkyl esters of sulfosuccinate salts such as sodium di(2- ethylhexyl) sulfosuccinate
  • sorbitol esters such as sorbitol oleate
  • quaternary amines such as lauryl trimethylammonium chloride
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
  • salts of mono and dialkyl phosphate esters such as mono and dialkyl phosphate esters.
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
  • biocidal active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
  • Pesticidal agents are referred to herein using their common name are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.
  • compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer).
  • SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
  • polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g., fertilizers or micronutrient donors or other preparations, which influence the growth of plants.
  • They can also be selective herbicides or non- selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • the polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient a polymorph as defined herein, in free form or in agrochemical usable salt form, and at least one of the above-mentioned adjuvants.
  • the invention therefore provides a composition, preferably a fungicidal composition, comprising a polymorph (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, an agriculturally acceptable carrier and optionally an adjuvant.
  • An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art.
  • said composition may comprise at least one or more pesticidal-active compounds, for example an additional fungicidal active ingredient in addition to the polymorph (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2- methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein.
  • pesticidal-active compounds for example an additional fungicidal active ingredient in addition to the polymorph (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2- methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein.
  • the polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide, or plant growth regulator where appropriate.
  • An additional active ingredient may, in some cases, result in unexpected synergistic activities.
  • Suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fung
  • suitable additional active ingredients include the following: petroleum oils, 1 ,1-bis(4- chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1- naphthylacetamide, 4-chlorophenyl phenyl sulfone, acetoprole, aldoxycarb, amidithion, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenous oxide, azobenzene, azothoate, benomyl, benoxa-fos, benzyl benzoate, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbanolate, carboxy
  • lecontei NPV, Orius spp. Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid, penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa, (E)-dec-5-en-1-yl acetate
  • suitable additional active ingredients are selected from the group consisting of benzovindiflupyr, fluxapyroxad, pydiflumetofen.isopyrazam, fluopyram, penthiopyrad, sedaxane, bixafen, difenoconazole, cyproconazole, tebuconazole, hexaconazole, prothioconazole, propiconazole, epoxiconazole, metconazole, tetraconazole, fluoxytioconazole, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]- 2-hydroxy-3-(1 , 2 ,4-tri azo I- 1 -yl)propanoate, methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy-1 -methyl-2- (1 ,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate, flutriafo
  • the compounds of the invention may also be used in combination with anthelmintic agents.
  • anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP-357460, EP-444964 and EP- 594291 .
  • Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO-9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
  • polymorphs of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
  • polymorphs of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO9615121 and also with anthelmintic active cyclic depsipeptides such as those described in WO961 1945, WO9319053, WO 9325543, EP-626375, EP-382173, WO-9419334, EP-382173, and EP-503538.
  • the polymorphs of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • ectoparasiticides for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
  • polymorphs of the invention may be used in combination with terpene alkaloids, for example those described in WO95/19363 or W004/72086, particularly the compounds disclosed therein.
  • Organophosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, me
  • Carbamates alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
  • Pyrethroids acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1 R)-cis-2,2-dimethyl-3-(2- oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a- cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenval
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
  • antiparasitics acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydr
  • Biological agents Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus, and fungi.
  • Bactericides chlortetracycline, oxytetracycline, streptomycin.
  • TX represents a crystalline polymorph form A of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate, or a crystalline polymorph form B of the compound methyl (Z)-2-(5-cyclohexyl- 2-methyl-phenoxy)-3-methoxy-prop-2-enoate, or a crystalline polymorph form C of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate: a compound selected from the group of substances consisting of
  • TX1 represent the compound methyl (E)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate: a composition selected from the group consisting of (4E,10Z)-tetradeca-4, 10-dienyl acetate + TX1 ; (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX1 ; (E)-6-methylhept-2-en-4-ol + TX1 ; (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX1 ; (E)-tridec-4-en-1-yl acetate + TX1 ; (S)-bioallethrin + TX1 ; (Z)-dodec-7-en-1-yl acetate + TX1 ; (Z)- hexadec-11
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, manco
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of acibenzolar-S-methyl, cyproconazole, difenoconazole, hexaconazole, prothioconazole, tebuconazole, fenpropidin, azoxystrobin, trifloxystrobin, mancozeb, chlorothalonil, fluazinam, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, metarylpicoxamid and metyltetraprole, or a salt, enantiomer, tautomer or N-oxide thereof
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of cyproconazole, difenoconazole, prothioconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil and flufenoxadiazam, or a salt, enantiomer, tautomer or N-oxide thereof.
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of difenoconazole, prothioconazole, tebuconazole, fenpropidin and chlorothalonil, or a salt, enantiomer, tautomer or N-oxide thereof.
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, manco
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, manco
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of acibenzolar-S-methyl, cyproconazole, difenoconazole, hexaconazole, prothioconazole, tebuconazole, fenpropidin, azoxystrobin, trifloxystrobin, mancozeb, chlorothalonil, fluazinam, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, metarylpicoxamid and metyltetraprole, or a salt, enantiomer, tautomer or N-oxide thereof
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of cyproconazole, difenoconazole, prothioconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil and flufenoxadiazam, or a salt, enantiomer, tautomer or N-oxide thereof.
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of difenoconazole, prothioconazole, tebuconazole, fenpropidin and chlorothalonil, or a salt, enantiomer, tautomer or N-oxide thereof.
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, manco
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, manco
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (C) as active ingredients, wherein component (B) is a compound selected from the group consisting of acibenzolar-S-methyl, cyproconazole, difenoconazole, hexaconazole, prothioconazole, tebuconazole, fenpropidin, azoxystrobin, trifloxystrobin, mancozeb, chlorothalonil, fluazinam, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, metarylpicoxamid and metyltetraprole, or a salt, enantiomer, tautomer or N-oxide thereof
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (C) as active ingredients, wherein component (B) is a compound selected from the group consisting of cyproconazole, difenoconazole, prothioconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil and flufenoxadiazam, or a salt, enantiomer, tautomer or N-oxide thereof.
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (C) as active ingredients, wherein component (B) is a compound selected from the group consisting of difenoconazole, prothioconazole, tebuconazole, fenpropidin and chlorothalonil, or a salt, enantiomer, tautomer or N-oxide thereof.
  • a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, manco
  • the weight ratio of component (A) to component (B) may be from 1000: 1 to 1 :1000, may be from 100:1 to 1 :100, preferably from 50:1 to 1 :50, more preferably from 20:1 to 1 :40, even more preferably from 15:1 to 1 :30, still more preferably from 12:1 to 1 :25, or from 10:1 to 1 :20, or from 10:1 to 1 :10, or from 5:1 and 1 :15, or from 5:1 to 1 :5, or from 4:1 to 1 :4, or from 3:1 to 1 :10, or from 3:1 to 1 :3, or from 2:1 to 1 :5, or 1 :1.
  • compositions used in the method of the invention comprising a mixture of components (A) and (B) are disclosed in Tables M1 and M2 below.
  • the composition may comprise an additional active ingredient component (C), which is different to component (B), and is selected from the group consisting of bixafen, fenpyrazamine, copper sulfate, copper hydroxide, triclopyricarb, acibenzolar, acibenzolar-S- methyl, copper oxychloride, copper oxide, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole,
  • the component (C) compounds are referred to herein and above by a so-called "ISO common name” or another "common name” being used in individual cases or a trademark name.
  • the component (C) compounds are known and are commercially available and/or can be prepared using procedures known in the art.
  • a fungicidal composition comprising a mixture of components (A), (B) and (C) as active ingredients, wherein component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, and wherein component (B) is the compound difenoconazole or prothioconazole; and wherein component (C) is a compound selected from the group consisting of cyproconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil, benzovindiflupyr and pydiflumetofen.
  • a fungicidal composition comprising a mixture of components (A), (B) and (C) as active ingredients, wherein component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, and wherein component (B) is the compound difenoconazole or prothioconazole; and wherein component (C) is a compound selected from the group consisting of cyproconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil, benzovindiflupyr and pydiflumetofen.
  • a fungicidal composition comprising a mixture of components (A), (B) and (C) as active ingredients, wherein component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, and wherein component (B) is the compound difenoconazole or prothioconazole; and wherein component (C) is a compound selected from the group consisting of cyproconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil, benzovindiflupyr and pydiflumetofen.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound mancozeb.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound prothioconazole.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound mancozeb.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound chlorothalonil.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound pydiflumetofen.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound mancozeb; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound chlorothalonil.
  • component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound cyproconazole.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound mancozeb.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound prothioconazole.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound mancozeb.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound chlorothalonil.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound pydiflumetofen.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound mancozeb; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound chlorothalonil.
  • component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound cyproconazole.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound mancozeb.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound prothioconazole.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound mancozeb.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound chlorothalonil.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound pydiflumetofen.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound mancozeb; and component (C) is the compound difenoconazole.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound chlorothalonil.
  • component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component
  • component (B) is the compound difenoconazole; and component (C) is the compound cyproconazole.
  • Components (B) and (C) in combination with component (A) may enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the fungicidal compositions may be effective against a wider spectrum of fungal pathogens that can be combated with the individual active ingredients when used solely.
  • the weight ratio of component (A) to the mixture of components (B) and (C) may be from 100:1 to 1 :100, or 50:1 to 1 :50, or 20:1 to 1 :20, or 10:1 to 1 :10, or 5:1 and 1 :5.
  • the weight ratio of component (A) to the mixture of components (B) and (C) may be from 2:1 to 1 :2, or 4:1 to 2:1 , or 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750.
  • Those mixing ratios are understood to include, on the one hand, ratios by weight and also,
  • composition comprise a component (A), a component (B) and a component (C), the weight ratio of component (A) to the sum of component (B) and component
  • (C) may be from 100:1 to 1 :100, preferably from 50:1 to 1 :50, more preferably from 20:1 to 1 :40, even more preferably from 15:1 to 1 :30, still more preferably from 12:1 to 1 :25, or from 10:1 to 1 :20, or from 10:1 to 1 :10, or from 5:1 and 1 :15, or from 5:1 to 1 :5, or from 4:1 to 1 :4, or from 3:1 to 1 :10, or from 3:1 to 1 :3, or from 2:1 to 1 :5, or 1 :1 .
  • compositions used in the method of the invention comprising a mixture of components (A), (B) and (C) are disclosed in Table M3 to M34 below, wherein the term ‘Form A’ refers to a crystalline polymorph, form A of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein.
  • a method of controlling or preventing infestation by phytopathogenic fungi preferably, Phakopsora pachyrhizi
  • a plant preferably, soybean
  • said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qo inhibitors
  • said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein the composition is a composition selected from the group consisting of M1.001 to M34.012 (as disclosed in Tables M1 to M34).
  • the preferred weight ratio of component A:B is as disclosed in tables R1 and R2.
  • a method of controlling or preventing phytopathogenic fungi, especially Corynespora cassiicola, on useful plants (preferably, soybean) or on propagation material thereof which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
  • a method of controlling or preventing phytopathogenic fungi especially Phakopsora (including Phakopsora ampelopsidis and Phakopsora pachyrhizi), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
  • phytopathogenic fungi especially Cercospora (including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf.
  • composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
  • Cercospora including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf.
  • Cercospora flagellaris, Cercospora janseana, Cercospora kikuchii, Cercospora lagenariae, Cercospora sojinae, Cercospora sorghi and Cercospora zeae-maydis), on useful plants (preferably, soybean) or on propagation material thereof, wherein said Cercospora comprises a G143A mutation in the mitochondrial cytochrome b which confers resistance to Qo inhibitors, said method comprising applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
  • Cercospora including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf.
  • Cercospora flagellaris, Cercospora janseana, Cercospora kikuchii, Cercospora lagenariae, Cercospora sojinae, Cercospora sorghi and Cercospora zeae-maydis), on useful plants (preferably, soybean) or on propagation material thereof, wherein said Cercospora comprises at least one of a E297K, I330T or P384S mutation in the CYP51 gene which confers resistance to sterol demethylation-inhibitors (DMI), said method comprising applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
  • a method of controlling or preventing phytopathogenic fungi especially Colletotrichum (including Colletotrichum acutatum, Colletotrichum cereale, Colletotrichum chrysanthemi, Colletotrichum cliviicola, Colletotrichum coccodes, Colletotrichum fragariae, Colletotrichum gloeosporioides, Colletotrichum graminicola, Colletotrichum lentis, Colletotrichum lindemuthianum, Colletotrichum musae, Colletotrichum orbiculare, Colletotrichum siamense and Colletotrichum truncatum), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to
  • a method of controlling or preventing phytopathogenic fungi especially Sclerotinia (including Sclerotinia minor, Sclerotinia borealis and Sclerotinia sclerotiorum), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
  • a method of controlling or preventing phytopathogenic fungi especially Septoria (including Septoria apiicola, Septoria glycines and Septoria lycopersici), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
  • a method of controlling or preventing phytopathogenic fungi especially Peronospora (including Peronospora destructor, Peronospora farinosa f. sp. spinaciae and Peronospora viciae f. sp. Pisi), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
  • a method of controlling or preventing phytopathogenic fungi especially Diaporthe (including Diaporthe amygdali, Diaporthe helianthin, Diaporthe neoviticola and Diaporthe phaseolorurri), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
  • the mixtures comprising a polymorph according to the invention, and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the polymorph according to the invention and the active ingredient(s) as described above, is not essential for working the present invention.
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient dosages are from 10mg to 1g of active substance per kg of seeds.
  • rates of 0.001 to 50 g of a compound of a polymorph per kg of seed, preferably from 0.01 to 10g per kg of seed are generally sufficient.
  • composition comprising a polymorph according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
  • the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of a polymorph according to the invention optionally together with other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • FIG. 1 shows the measured powder X-ray diffraction pattern of the polymorph form A of the invention.
  • FIG. 2 shows the measured powder X-ray diffraction pattern of the polymorph form B of the invention.
  • FIG. 3 shows the predicted powder X-ray diffraction pattern of the polymorph form C of the invention.
  • FIG. 4 shows a DSC trace of the polymorph form A of the invention.
  • FIG. 5 shows a DSC trace of the polymorph form B of the invention.
  • FIG. 6 shows the predicted ideal solubility (as a solubility vs. temperature plot) of polymorphs form A and form B of the invention
  • the polymorph of the invention was made by adding ethanol to (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)- 3-methoxy-prop-2-enoate and left to stir for at least 30 minutes to ensure dissolution. The sample was then allowed to undergo evaporative crystallisation. The resulting crystals were ground using a pestle and mortar and X-ray diffraction analysis (PXRD) confirmed the presence of the polymorph, form A, of the invention.
  • PXRD X-ray diffraction analysis
  • the polymorph of the invention was made by purifying (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate by flash chromatography with Ethyl acetate/Cyclohexane solution resulting in the crystals nucleating.
  • X-ray diffraction analysis confirmed the presence of the polymorph, form B, of the invention.
  • the compound of formula I was made according to the methods described in WO 2022/200579.
  • the polymorph of the invention was made by adding dimethyl carbonate to (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate and left to stir for at least 30 minutes to ensure dissolution. The sample was then allowed to undergo evaporative crystallisation. A single crystal was then analysed by X-ray diffraction (SCXRD) at 100 K (-173 °C) confirmed the presence of the polymorph, form C, of the invention.
  • SCXRD X-ray diffraction
  • the samples were subject to analysis by powder X-ray diffraction (PXRD) and/or single crystal X-ray diffraction (SCXRD) and/or differential scanning calorimetry (DSC).
  • PXRD powder X-ray diffraction
  • SCXRD single crystal X-ray diffraction
  • DSC differential scanning calorimetry
  • Powder X-ray diffraction analysis of solid material was carried out using the Malvern Panalytical Empyrean powder X-ray diffractometer at room temperature. Samples were ground using a marble pestle and mortar for 4 minutes and packed onto a zero-background silicon wafer disc and the surface of the sample levelled with a microscope slide. The pXRD holder was placed in the instrument, spun (rotation time: 2s) and the powder pattern collected from 3.0° to 40° 2-theta with 0.0167° step size and 23s exposure time.
  • Measured powder X-ray diffraction patterns for the polymorphs of the invention form A and form B are shown in FIG. 1 and FIG. 2, respectively.
  • DSC Differential scanning calorimetry

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Abstract

The invention relates to crystalline forms of compounds of methyl (Z)-2-(5-cyclohexyl-2-methyl-5 phenoxy)-3-methoxy-prop-2-enoate, compositions comprising said crystalline forms and methods of their use as fungicides.

Description

POLYMORPHS OF A METHOXYACRYLATE DERIVATIVE
The present invention relates to solid forms of substituted meth oxacry late derivatives, compositions comprising the solid forms and methods of their use as fungicides.
W02020/193387, WO2021/176057 and W02022/200579 describe the use of methoxyacrylate derivatives for combating phytopathogenic fungi and methods for preparing said methoxyacrylate derivatives, in particular methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, shown below,
Figure imgf000002_0001
New solid forms of this compound, their compositions and methods of their preparation and use have now been discovered.
According to the present invention, in one embodiment there is provided a novel crystalline polymorphic form of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, designated ‘form A’.
In a first aspect of the invention there is provided a crystalline polymorph, form A of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.0° ± 0.2°, 18.6° ± 0.2°, 20.3° ± 0.2° and 22.0° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
In another embodiment, there is provided a novel crystalline polymorphic form of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, designated ‘form B’.
According to a second aspect of the invention there is provided a crystalline polymorph, form B of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.2° ± 0.2°, 18.7° ± 0.2°, 20.4° ± 0.2° and 24.4° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
In another embodiment, there is provided a novel crystalline polymorphic form of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, designated ‘form C’. According to a third aspect of the invention, there is provided a crystalline polymorph form C of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.1 ° ± 0.2°, 19.5° ± 0.2°, 20.7° ± 0.2° and 22.3° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .54184 A.
According to a fourth aspect of the invention, there is provided an agrochemical composition comprising a crystalline polymorph form A, or form B, or form C, of the compound methyl (Z)-2-(5-cyclohexyl-2- methyl-phenoxy)-3-methoxy-prop-2-enoate and an agrochemically acceptable carrier or diluent.
According to a fifth aspect of the invention, there is provided a method of controlling or preventing infestation by phytopathogenic fungi in a plant, wherein a fungicidally effective amount of a crystalline polymorph form A, or form B, or form C, of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate, or a composition comprising said polymorph as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
According to a sixth aspect of the invention, there is provided a method of controlling or preventing infestation by phytopathogenic fungi in a plant, wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qol inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a polymorph as described herein, or a composition comprising said polymorph as active ingredient.
The crystalline polymorph of the invention designated form A may be characterised by the unit cell parameters of its single crystal as shown below in Table 1. The polymorph was obtained using the method described in Example 1 .
Table 1
Figure imgf000003_0001
In the table a, b, c = Length of the edges of the unit cell and a, p, y = Angles of the unit cell.
Thus, in one embodiment of the present invention, the crystalline polymorph (form A) of the invention has the following lattice parameters: a = 12.7 A ± 0.1 , b = 1 1 .0 A ± 0.1 , c = 13.1 A ± 0.1 , a = 90.0° ± 0.2°, p = 1 10.2° ± 0.2°, y = 90.0°± 0.2° and volume = 1706.6 A3 ± 17 A3.
The crystalline polymorph (form A) may also be characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles or d spacings. Thus, in another embodiment of the invention, the crystalline polymorph (form A) of the invention has a powder X-ray diffraction pattern comprising peaks at 12.0° ± 0.2°, 18.6° ± 0.2°, 20.3° ± 0.2° and 22.0° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength (Cu Ka) of 1 .5406 A. Preferably, the polymorph further exhibits peaks at 16.5° ± 0.2°, 18.2° ± 0.2°, 23.5° ± 0.2°, 24.7° ± 0.2° and 26.6° ± 0.2° 20. More preferably, the polymorph further exhibits peaks at 14.9° ± 0.2°, 16.9° ± 0.2°, 17.7° ± 0.2°, 21.5° ± 0.2°, 21.8° ± 0.2°, 24.5° ± 0.2° and 27.4° ± 0.2° 20.
In a preferred embodiment of the invention the crystalline polymorph (form A) of the invention has a powder X-ray diffraction pattern comprising peaks at 12.0° ± 0.2°, 16.5° ± 0.2°, 18.2° ± 0.2°, 18.6° ± 0.2°, 20.3° ± 0.2°, 22.0° ± 0.2°, 23.5° ± 0.2°, 24.7° ± 0.2° and 26.6° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
In another preferred embodiment of the invention the crystalline polymorph (form A) of the invention has a powder X-ray diffraction pattern comprising peaks at 12.0° ± 0.2°, 14.9° ± 0.2°, 16.5° ± 0.2°, 16.9° ± 0.2°, 17.7° ± 0.2°, 18.2° ± 0.2°, 18.6° ± 0.2°, 20.3° ± 0.2°, 21.5° ± 0.2°, 21.8° ± 0.2°, 22.0° ± 0.2°, 23.5° ± 0.2°, 24.5° ± 0.2°, 24.7° ± 0.2°, 26.6° ± 0.2° and 27.4° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
In another preferred embodiment of the invention the crystalline polymorph (form A) of the invention has a powder X-ray diffraction pattern comprising the peaks substantially as shown in figure 1 and listed in table 2 below (along with the corresponding d spacing and relative intensity values):
Table 2 - PXRD peak list table for form A of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate
Figure imgf000004_0001
Figure imgf000005_0001
In another embodiment of the invention there is provided a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, wherein the polymorph has a melting point of from 101 °C to 107 °C (preferably, from 101 °C to 106 °C, more preferably, 102 °C to 106 °C and even more preferably, 102 °C to 105 °C). This melting point is obtained using Differential Scanning Calorimetry (DSC) with a heating rate of 10 °C/minute. A further crystalline polymorph, of the invention designated form B may be obtained using the method described in Example 2.
The crystalline polymorph (form B) may also be characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles or d spacings. Thus, in another embodiment of the invention, there is provided a crystalline polymorph form B of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate, wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.2° ± 0.2°, 18.7° ± 0.2°, 20.4° ± 0.2° and 24.4° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A. Preferably, the polymorph further exhibits peaks at 8.4° ± 0.2°, 10.2° ± 0.2°, 18.5° ± 0.2°, 22.1 ° ± 0.2°, 22.9° ± 0.2°, 23.7° ± 0.2° and 24.9° ± 0.2° 20. More preferably, the polymorph further exhibits peaks at 15.9° ± 0.2°, 17.4° ± 0.2°, 18.2° ± 0.2°, 23.3° ± 0.2° and 27.6° ± 0.2° 20.
In a preferred embodiment of the invention the crystalline polymorph (form B) of the invention has a powder X-ray diffraction pattern comprising peaks at 8.4° ± 0.2°, 10.2° ± 0.2°, 12.2° ± 0.2°, 18.5° ± 0.2°, 18.7° ± 0.2°, 20.4° ± 0.2°, 22.1 ° ± 0.2°, 22.9° ± 0.2°, 23.7° ± 0.2°, 24.4° ± 0.2° and 24.9° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
In another preferred embodiment of the invention the crystalline polymorph (form B) of the invention has a powder X-ray diffraction pattern comprising peaks at 8.4° ± 0.2°, 10.2° ± 0.2°, 12.2° ± 0.2°, 15.9° ± 0.2°, 17.4° ± 0.2°, 18.2° ± 0.2°, 18.5° ± 0.2°, 18.7° ± 0.2°, 20.4° ± 0.2°, 22.1 ° ± 0.2°, 22.9° ± 0.2°, 23.3° ± 0.2°, 23.7° ± 0.2°, 24.4° ± 0.2°, 24.9° ± 0.2° and and 27.6° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
In another preferred embodiment of the invention the crystalline polymorph (form B) of the invention has a powder X-ray diffraction pattern comprising the peaks substantially as shown in figure 2 and listed in table 3 below (along with the corresponding d spacing and relative intensity values):
Table 3 - PXRD peak list table for form B of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000008_0001
In another embodiment of the invention there is provided a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, wherein the polymorph has a melting point of from 94 °C to 98 °C (preferably, from 95 °C to 97 °C). This melting point is obtained using Differential Scanning Calorimetry (DSC) with a heating rate of 10 °C/minute.
A further crystalline polymorph, of the invention designated form C may obtained using the method described in Example 3.
The crystalline polymorph (form C) may also be characterised by a powder X-ray diffraction pattern expressed in terms of 20 angles or d spacings. Thus, in another embodiment of the invention, there is provided a crystalline polymorph form C of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate, wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.1 ° ± 0.2°, 19.5° ± 0.2°, 20.7° ± 0.2° and 22.3° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1.54184 A. Preferably, the polymorph further exhibits peaks at at 8.9° ± 0.2°, 16.4° ± 0.2°, 17.6° ± 0.2°, 18.1 ° ± 0.2°, 21.4° ± 0.2°, 24.9° ± 0.2° and 25.0° ± 0.2° 20. More preferably, the polymorph further exhibits peaks at 15.7° ± 0.2°, 24.3° ± 0.2°, 26.5° ± 0.2°, 27.6° ± 0.2°, 28.1 ° ± 0.2° 20 and 28.6° ± 0.2° 20.
In a preferred embodiment of the invention the crystalline polymorph (form C) of the invention has a powder X-ray diffraction pattern comprising peaks at 8.9° ± 0.2°, 12.1 ° ± 0.2°, 16.4° ± 0.2°, 17.6° ± 0.2°, 18.1 ° ± 0.2°, 19.5° ± 0.2°, 20.7° ± 0.2°, 21.4° ± 0.2°, 22.3° ± 0.2° 20, 24.9° ± 0.2° and 25.0° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .54184 A.
In another preferred embodiment of the invention the crystalline polymorph (form C) of the invention has a powder X-ray diffraction pattern comprising peaks at 8.9° ± 0.2°, 12.1 ° ± 0.2°, 15.7° ± 0.2°, 16.4° ± 0.2°, 17.6° ± 0.2°, 18.1 ° ± 0.2°, 19.5° ± 0.2°, 20.7° ± 0.2°, 21.4° ± 0.2°, 22.3° ± 0.2° 20, 24.3° ± 0.2°, 24.9° ± 0.2°, 25.0° ± 0.2°, 26.5° ± 0.2°, 27.6° ± 0.2°, 28.1 ° ± 0.2° 20 and 28.6° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .54184 A.
In another preferred embodiment of the invention the crystalline polymorph (form C) of the invention has a powder X-ray diffraction pattern comprising the peaks substantially as shown in figure 3 and listed in table 4 below (along with the corresponding d spacing and relative intensity values):
Table 4 - PXRD predicted pattern peak list table for form C of the compound methyl (Z)-2-(5-cyclohexyl- 2-methyl-phenoxy)-3-methoxy-prop-2-enoate
Figure imgf000009_0001
Figure imgf000010_0001
The crystalline polymorph of the invention designated form C may also be characterised by the unit cell parameters of its single crystal as shown below in Table 5. The polymorph was obtained using the method described in Example 1 .
Table 5
Figure imgf000010_0002
In the table a, b, c = Length of the edges of the unit cell and a, p, y = Angles of the unit cell.
Thus, in one embodiment of the present invention, the crystalline polymorph (form C) of the invention has the following lattice parameters: a = 11.8 A ± 0.1 , b = 11 .3 A ± 0.1 , c = 12.8 A ± 0.1 , a = 90.0° ± 0.2°, p = 107.5° ± 0.2°, y = 90.0°± 0.2° and volume = 1631 .1 A3 ± 16 A3.
Brief Description of the Drawings
Figure 6 - shows the predicted ideal solubility (as a solubility vs. temperature plot) of polymorphs form A and form B of the invention using the melting point and heat of fusion data for the different polymorphs and using a non-linear Van’t Hoff equation as reported in the International Journal of Pharmaceutics, 18 (1984) 25-38. It is also well known that the Van’t Hoff equation can be used to determine thermodynamic stability of different polymorphs, see Crystal Growth & Design, Vol.3, No.6, 2003. Thus the predicted ideal solubility can be calculated as follows: x = exp(-AHf/R * (1/T - 1/Tm)) where x: soluble mole fraction exp: exponential function
AHf: heat of fusion (J/mol) (obtained from DSC data)
R: gas constant (8.314 J/mol K)
T: temperature of interest (K)
Tm: melting point (K) (obtained from DSC data)
When using the disclosed thermal data obtained for claimed polymorphs, form A and form B it can be seen from the solubility vs. temperature plot (Fig 6) that form A is the monotropic stable polymorph compared to form B. For agrochemical products to avoid failures arising from polymorphic transformations it is desired to have the less soluble and more thermodynamically stable form, in this case form A.
In the context of the present invention, a polymorph is a particular crystal form of a chemical compound that can exist in more than one crystal form in the solid state. A crystal form of a compound contains the consitituent molecules arranged in orderly repeating patterns extending in all three spatial dimensions (in contrast, an amorphous solid form has no long-range order in the position of molecules). Different polymorphs of a compound have different arrangements of atoms and or molecules in their crystal structure. When the compound is a biologically active compound, such as a fungicide, the difference in crystal structures can lead to different polymorphs having differing chemical, physical and biological properties. Properties which may be affected include crystal shape, density, hardness, colour, chemical stability, melting point, hydroscopicity, suspensibility, dissolution rate and biological availability. As such, a specific polymorph may have properties which make it more advantageous in a particular use relative to another polymorph of the same compound: in particular, the physical, chemical and biological properties listed above and have a significant effect on the development of production methods and formulations, the ease with which a compound can be combined in a formulation with other active ingredients and formuation components and the quality and efficacy of plant treatment agents, such as fungicides. It is noted that predicting whether the solid state of a compound may be present as more than one polymorph is not possible and nor is it possible to predict the properties of any of these crystal forms.
In particular, the use of a specific polymorph may allow the use of new formulations compared with existing polymorphic/amorphous forms of a compound. This might be advantageous for a number of reasons. For example, a suspension concentrate (SC) formulation may be preferred over an emulsion concentrate (EC) because the lack of solvent in the SC often means that the formulation is likely to be less phytotoxic than an equivalent EC formulation - however, if the existing form of a compound is not stable in such an SC formulations, polymorphic conversion might occur leading to unwanted crystal growth. Such crystal growth is detrimental because it leads to, for example, thickening and potentially solidification of the formulation which can lead to blockages in application equipment, e.g in spray nozzles in agricultural application machinery. Using a stable polymorphic form would overcome these issues.
Assaying the solid phase for the presence of crystals may be carried out be conventional methods known in the art. For example, it is convenient and routine to use powder X-ray diffraction techniques. Othertechniques which may be used include differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and Raman or Infra-red spectroscopy, NMR, gas chromatography or HPLC. Single crystal X-ray diffraction is especially useful in identifying crystal structures.
The polymorph of the invention may be applied in unchanged form but is more preferably incorporated into agrochemical compositions by conventional means. Accordingly, in a further aspect, the invention provides an agrochemical composition comprising the polymorph of the invention as defined above and at least one agriculturally acceptable carrier or diluent.
In one embodiment, there is provided an agrochemical composition comprising a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein and an agrochemically acceptable carrier or diluent.
In another embodiment, there is provided an agrochemical composition comprising a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein and an agrochemically acceptable carrier or diluent.
In another embodiment, there is provided an agrochemical composition comprising a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein and an agrochemically acceptable carrier or diluent.
In another embodiment of the invention, there is provided a method of controlling or preventing infestation by phytopathogenic fungi in a plant, wherein a fungicidally effective amount of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, or a composition comprising said polymorph as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
In another embodiment of the invention, there is provided a method of controlling or preventing infestation by phytopathogenic fungi in a plant, wherein a fungicidally effective amount of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, or a composition comprising said polymorph as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
In another embodiment of the invention, there is provided a method of controlling or preventing infestation by phytopathogenic fungi in a plant, wherein a fungicidally effective amount of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, or a composition comprising said polymorph as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
In one embodiment of the invention, there is provided a method of controlling or preventing infestation by phytopathogenic fungi in a plant, wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qol inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidally effective amount of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, or a composition comprising said polymorph as active ingredient.
In another embodiment of the invention, there is provided a method of controlling or preventing infestation by phytopathogenic fungi in a plant, wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qol inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidally effective amount of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate as defined herein, or a composition comprising said polymorph as active ingredient.
In another embodiment of the invention, there is provided a method of controlling or preventing infestation by phytopathogenic fungi in a plant, wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qol inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidally effective amount of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate as defined herein, or a composition comprising said polymorph as active ingredient.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate according to the invention can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man. The novel polymorphs are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants. The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.
The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein a fungicidally effective amount of a crystalline polymorph form A, or form B, or form C of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate is applied to the plants, to parts thereof or the locus thereof.
In one embodiment, the present invention relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein a fungicidally effective amount of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to the plants, to parts thereof or the locus thereof.
In another embodiment, the present invention relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein a fungicidally effective amount of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to the plants, to parts thereof or the locus thereof.
In another embodiment, the present invention relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein a fungicidally effective amount of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to the plants, to parts thereof or the locus thereof.
The term “fungicide” as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term “fungicidally effective amount” means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection. The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
The term "plant propagation material” denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants.
The term “locus” as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
Furthermore, the polymorphs (form A, orform B, orform C) of the compound methyl (Z)-2-(5-cyclohexyl- 2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.
In addition, the invention could be used to protect non-living materials from fungal attack, e.g., lumber, wall boards and paint.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein and/or agrochemical compositions comprising the polymorph of the present invention are effective in controlling a broad spectrum of plant diseases, such as foliar and/or soil-borne pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.
These pathogens may include:
Oomycetes, including Phytophthora species such as Phytophthora cactorum, Phytophthora capsici, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, Phytophthora erythrose ptica, Phytophthora fragariae, Phytophthora infestans, Phytophthora nicotianae, Phytophthora porri, and Phytophthora sojae; Pythium species such as Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; other Peronosporales such as Bremia lactucae, Hyaloperonospora parasitica, Hyaloperonospora brassicae, Sclerophthora macrospora, Sclerospora graminicola Peronospora species including Peronospora destructor, Peronospora farinosa f. sp. spinaciae and Peronospora viciae f. sp. pisi; Plasmopara species including Plasmopara halstedii and Plasmopara viticola; Pseudoperonospora species including Pseudoperonospora cubensis and Pseudoperonospora humili; Peronosclerospora species including Peronosclerospora maydis, Peronosclerospora philippinensis and Peronosclerospora sorghi; Albuginales such as Albugo Candida, Albugo occidentalis, and Albugo tragopogonis; and Saprolegniales such as Aphanomyces species, including Aphanomyces cochliodes.
Ascomycetes, including Mycosphaerellales such as Actinothyrium graminis, Asperisporium caricae, Cercospora species including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf. flagellaris, Cercospora janseana, Cercospora kikuchii, Cercospora lagenariae, Cercospora sojinae, Cercospora sorghi, Cercospora zeae-maydis; Dothistroma septosporum, Fulvia fulva, Mycosphaerella species including Mycosphaerella pomi and Mycosphaerella linicola; Neopseudocercosporella brassicae, Neopseudocercosporella capsellae, Nothopassalora personata, Nothophaeocrytopus gaeumannii, Passalora bataticola, Passalora koepkei, Pseudocercospora griseola, Pseudocercospora musaei, Pseudocercospora vitis, Pseudocercospora fijiensis, Ramularia species including Ramularia beticola and Ramularia collo-cygni; Ramulariopsis gossypii, Ramulariopsis pseudoglycines, Ramulispora sorghi, Scolecostigmina palmivora, Septoria species including Septoria apiicola, Septoria glycines and Septoria lycopersici; Zasmidium citri-griseum, and Zymosepotria tritici; Helotiales such as Blumeriella jaapii, Botrytis species including Botrytis cinerea, Botrytis aclada and Botrytis fabae; Botryotinia squamosa, Cadophora gregata, Civorinia aim, Claireedia homoeocarpa, Diplocarpon coronariae, Diplocarpon rosae, Drepanopeziza campestris, Gloeotinia temulenta, Hymenoscyphus fraxineus, Leptotrochila medicaginis, Marssonina graminicola, Monilinia species including Monilinia fructicola, Monilinia fructigena and Monilinia laxa; Neofabraea perennans, Neofabraea vagabunda, Oculimacula yallundae, Pezicula spp., Pseudopeziza medicaginis, Pseudopeziza tracheiphila, Pyrenopeziza species including Pyrenopeziza brassicae; Rhabdocline pseudotsugae, Rhynchosporium species including Rhynchosporium secalis; Sclerotinia species including Sclerotinia minor, Sclerotinia borealis and Sclerotinia sclerotiorum; Hypocreales such as Acremonium strictum, Albifimbria verrucaria, Claviceps africana, Claviceps purpurea, Fusarium species including Fusarium avenaceum, Fusarium culmorum, Fusarium fujikuroi, Fusarium graminearum, Fusarium incarnatum, Fusarium langsethiae, Fusarium moniliforme, Fusarium oxysporum, Fusarium oxysporum f.sp. cubense, Fusarium poae, Fusarium proliferatum, Fusarium pseudograminearum, Fusarium subglutinans, Fusarium sulphureum, Fusarium tricinctum and Fusarium verticillioides; Gliocladium spp., Neocosmospora phaseoli, Neocosmospora solani, Neonectria Candida, Paramyrothecium roridum, Sarocladium oryzae, Trichoderma species including Trichoderma harzianum, Trichoderma pseudokoningii and Trichoderma viride; Trichothecium roseum and Ustilaginoidea virens; Magnaporthales such as Gaeumannomyces avenae, Gaeumannomyces graminis, Gaeumannomyces graminis tritici, Gaeumannomyces wongoonoo, Magnaporthiopsis poae, Pyricularia species including Pyricularia grisea and Pyricularia oryzae; Pleosporales, such as Altemaria species including Altemaria aim, Altemaria alternata, Altemaria arachidis, Altemaria brassicae, Alternaria brassicicola, Altemaria citri, Altemaria dauci, Altemaria grandisi, Altemaria helianthicola, Altemaria linariae, Altemaria mali, Altemaria porri, Altemaria solani and Altemaria tomato; Boeremia coffeae, Ascochyta species including Ascochyta pisi and Ascochyta rabiei; Bipolaris maydis, Bipolaris oryzae, Bipolaris sorokiniana, Cochliobolus spp., Corynespora cassiicola, Curvularia species including Curvularia australiensis, Curvularia cactivora and Curvularia lunata; Didymella species including Didymella pinodella and Didymela pinodes; Xenodidymella applanata, Drechslera species including Drechslera glycines; Epicoccum nigrum, Exserohilum turcicum, Helminthosporium species including Helminthosporium solani; Hendersonia creberrima, Leptosphaerulina crassiasca, Neocamarosporium betae, Ophiosphaerella agrostidis, Ophiosphaerella herpotricha, Ophiosphaerella korrae, Ophiosphaerella narmari, Parastagonospora nodorum, Phaeosphaeria herpotrichoides, Phaerosphaeria maydis, Phoma spp., Plenodomus lindquistii, Plenodomus lingam, Pleospora spp., Pseudopyrenochaeta lycopersici, Pyrenophora species including Pyrenophora poae, Pyrenophora teres and Pyrenophora tritici-repentis; Remotididymella destructiva, Stagonospora tainanensis, Stagonosporopsis cucurbitacearum, Stemphylium species including Stemphylium botryosum, Stemphylium solani and Stemphylium vesicarium; Diaporthales such as Anisogramma anonmala, Apiognomonia errabunda, Cytospora platani, Diaporthe species including Diaporthe amygdali, Diaporthe helianthin, Diaporthe neoviticola and Diaporthe phaseolorum; Dicarpella spp., Discula destructiva, Gnomoniopsis fructicola, Greeneria uvicola, Juglanconis juglandina, Ophiognomonia clavigignenti-juglandacearum, Stenocarpella maydis and Tubakia dryina; Dothideales such as Aureobasidium species including Aureobasidium pullulans; Discosphaerina fulvida; Erysiphales such as Blumeria graminis, Brasiliomyces malachrae, Erysiphe species including Erysiphe betae, Erysiphe cruciferarum, Erysiphe diffusa, Erysiphe heraclei, Erysiphe necator and Erysiphe pisi; Golovinomyces cichoracearum, Golovinomyces orontii, Leveillula taurica, Oidium arachidisi, Oidium neolycoperisci, Phyllactinia guttata, Podosphaera species including Pososphaera aphanis, Podosphaera fuliginea, Podosphaera fusca, Podosphaera leucotricha, Podosphaera macularis, Podosphaera mors-uvae, Podosphaera pannosa, Podosphaera tridactyla and Podosphaera xanthii; Glomerellales such as Colletotrichum species including Colletotrichum acutatum, Colletotrichum cereale, Colletotrichum chrysanthemi, Colletotrichum cliviicola, Colletotrichum coccodes, Colletotrichum fragariae, Colletotrichum gloeosporioides, Colletotrichum graminicola, Colletotrichum lentis, Colletotrichum lindemuthianum, Colletotrichum musae, Colletotrichum orbiculare, Colletotrichum siamense and Colletotrichum truncatum; Glomerella cingluata, Glomerella gossypii, Musicillium theobromae, Plectosphaerella cucumerina, Verticillium species including Verticillium dahlia; Venturiales such as Venturia species including Venturia carpophila, Venturia effusa, Venturia inaequalis, Venturia oleaginea, and Venturia pyrina; Xylariales such as Eutypa lata, Microdochium albescens, Microdochium majus, Microdochium nivale, Microdochium paspali, Microdochium sorghi, Physalospora abdita, Rosellinia spp. and Seimatosporium mariae; Botryosphaeriales such as Botryosphaeria species including Botryosphaeria dothidea; Diplodia species including Diplodia seriata; Dothiorella aromatica, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta ampelicida and Phyllosticta cucurbitacearum; Eurotiales such as Aspergillus species including Aspergillus flavus, Aspergillus fumigatus, Aspergillus niger and Aspergillus terreus; Penicillium species including Penicillium digitatum, Penicillium expansum and Penicillium italicum; Microascales such as Berkeleyomyces basicola, Thielaviopsis paradoxa, Ceratocystis species including Ceratocystis fimbriata, Ceratocystis manginecans and Ceratocystis platani; Scedosporium species including Scedosporium apiospermum and Scedosporium prolificans; Myriangiales such as Elsinoe species including Elsinoe ampelina and Elsinoe perseae; Ophiostomatales such as Leptographium lundbergii, Leptographium microsporum, Ophiostoma novo-ulmi, Ophiostoma piceae and Sporothrix spp.; Pezizomycetes such as Phymatotrichopsis omnivore and Polyscytalum pustulans; Phyllachorales such as Gibellina cerealis, Phyllachora maydis and Phyllachora pomigena; Amphisphaeriales such as Griphosphaeria corticola, Lepteutypa cupressi and Pestalotia rhododendri; Capnodiales such as Capnodium ramosum and Schizothyrium pomi; Chaetothyriales such as Phialophroa spp.; Cladosporiales such as Cladosporium species including Cladosporium oxysporum, Cladosporium cucumerinum and Cladosporium allii-cepae; Rhytismatales such as Lophodermium seditiosum and Naemacyclus spp.; Saccharomycetales such as Cephaloascus species including Cephaloascus fragrans; Geotrichum candidum, Candida species including Candida glabrata, Candida krusei, Candida lusitaniae, Candida parapsilosis, Candida albicans and Candida tropicalis; Sordariales such as Chaetomium spp. and Monosporascus cannonballus; Sordariomycetes such as Wongia garrettii and Wongia griffinii; Taphrinales such as Taphrina bullata and Taphrina deformans; Onygenales such as Ajellomyces capsulatus, Blastomyces dermatitidis, Coccidioides species including Coccidioides immitis; Epidermophyton spp., Histoplasma spp., Microsporum spp., Trichophyton spp., and Paracoccidioides species including Paracoccioides brasiliensis; and others such as Hymenula cerealis, Petriellidum spp., and Septocyta ruborum.
Basidiomycetes, including Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Cron art! urn ribicola, Gymnosporangium juniperi-virginianae, Gymnosporangium sabinae, Hemileia species including Hemileia vastatrix; Melampsora medusae, Melampsora lini, Phakopsora ampelopsidis, Phakopsora pachyrhizi, Phragmidium mucronatum, Puccinia species including Puccinia aim, Puccinia arachidis, Puccinia asparagi, Puccinia cacabata, Puccinia coronata, Puccinia graminis, Puccinia helianthi, Puccinia hieracii, Puccinia horde! , Puccinia horiana, Puccinia melanocephala, Puccinia polysora, Puccinia porri, Puccinia recondita, Puccinia sorghi, Puccinia striiformis, Puccinia striiformis f.sp. horde!, Puccinia striiformis f.sp. tritici and Puccinia triticina; Pucciniastrum coryli, Tranzschelia discolor, Uromyces species including Uromyces betae, Uromyces pis! and Uromyces viciae-fabae; Tilletiales such as Neovossia moliniae, and Tilletia species including Tilletia caries and Tilletia controversa; Ustilaginales such as Sporisorium reilianum and Ustilago species including Ustilago maydis, Ustilago segetum var. nuda, Ustilago segetum var. tritici and Ustilago striiformis; Urocystidales such as Urocystis species including Urocystis agropyri; Agaricales such as Marasmiellus inoderma, Mycena spp., Moniliophthora roreri and Moniliophthora perniciosa; Cantharellales such as Sclerotium spp. and Typhula species including Typhula incarnata and Typhula ishikariensis; Ceratobasidiales such as Waitea circinata, and Rhizoctonia species including Rhizoctonia cerealis, Rhizoctonia solan! and Rhizoctonia theobromae; Atheliales such as Athelia rolfsii; Corticiales such as Corticium invisum and Laetisaria fuciformis; Cystodilobasidiales such as Itersonilia perplexans; Entylomatales such as Entyloma calendulae f.sp. dahliae and Entylomella microspore; Exobasidiales such as Exobasidium vexans; Hymenochaetales such as Phellinus igniarius; Russulales such as Stereum hirsutum; and Tremellales such as Cryptococcus species including Cryptococcus neoformans.
Zygomycetes, including Mucorales such as Choanephora cucurbitarum, Mucor spp., Rhizopus oryzae, Absidia corymbifera and Rhizomucor pusillus.
Blastocladiomycetes, including Physoderma maydis. as well as diseases caused by other species and genera closely related to those listed above.
In addition to their fungicidal activity, the compositions may also have activity against diseases caused by Actinobacteria such as Streptomyces scabiei; Proteobacteria such as Erwinia amylovora, Pectobacterium carotovorum, Xanthomonas species including Xanthomonas axonopodis, Xanthomonas campestris, Xanthomonas citri, Xanthomonas oryzae and Xanthomonas vesicatoria Xylella fastidiosa, and Pseudomonas species including Pseudomonas syringae Cercozoa such as Polymyxa betae, Polymyxa graminis and Spongospora subterranea; and Bigyra such as Labyrinthula zosterae. as well as diseases caused by other species and genera closely related to those listed above.
The polymorphs of the present invention as disclosed herein are particularly effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (also known as Deuteromycetes; e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella); Oomycetes (e.g. Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara).
In preferred embodiments, the polymorphs (form A, or form B, or form C) of the compound methyl (Z)- 2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), can be used on the following crops and pathogens:
Preferably, the polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl- 2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), are suitable for controlling the following fungal diseases on soybeans and genetically modified soybeans, for example Bt soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (Cercospora leaf spots), e.g., C. sojina or C. kikuchii Colletotrichum (teleomorph: Glomerella) spp. (anthracnose), e.g., C. truncatum or C. gloeosporioides)', Corynespora cassiicola (leaf spots); Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot); Diaporthe spp., e.g., D. phaseolorum (damping off); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot), e.g. F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans; Macrophomina phaseolina (syn. phaseoli) (root and stem rot); Microsphaera diffusa (powdery mildew); Peronospora spp. (downy mildew), e.g., P. manshurica; Phakopsora pachyrhizi and P. meibomiae (soybean rust); Phialophora spp., e.g., P. g reg ata', stem rot; Phomopsis spp., e.g., stem rot: P. phaseoli (teleomorph: Diaporthe phaseolorum)’, Pythium spp. (damping-off); Phytophthora spp. (wilt, root, leaf, fruit and stem root), e.g., P. megasperma, syn. P. sojae)', Rhizoctonia spp., e.g., R. solani (root and stem rot); Sclerotinia spp. (stem rot or white mold); Septoria spp., e.g., S. glycines (brown spot); S. rolfsii (syn. Athelia rolfsii); Thielaviopsis spp. (black root rot).
More preferably, the polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), are suitable for controlling the following fungal diseases on soybeans and genetically modified soybeans, for example Bt soybeans: Alternaria spp. (Alternaria leaf spot); Cercospora spp. (Cercospora leaf spots), e.g., C. sojina or C. kikuchii); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose), e.g., C. truncatum or C. gloeosporioides); Corynespora cassiicola (leaf spots); Diaporthe spp., e.g., D. phaseolorum (damping off); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot), e.g. F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans; Mac- rophomina phaseolina (syn. phaseoli) (root and stem rot); Peronospora spp. (downy mildew), e.g., P. manshurica ; Phakopsora pachyrhizi and P. meibomiae (soybean rust); Phomopsis spp., e.g., stem rot: P. phaseoli (teleomorph: Diaporthe phaseolorum); Phytophthora spp. (wilt, root, leaf, fruit and stem root), e.g., P. megasperma, syn. P. sojae); Rhizoctonia spp., e.g., R. solani (root and stem rot); Septoria spp., e.g., S. glycines (brown spot).
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), according to the present invention are particularly important for controlling phyto- pathogenic harmful fungi on soybeans and genetically modified soybeans, for example Bt soybeans.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, and mixtures thereof (as listed below), according to the present invention are also particularly important for controlling Phakopsora pachyrhizi, P. meibomiae (soybean rust), Cercospora sojina, Cercospora kikuchii, Corynospera cassiicula, Colletotrichum truncatum, Sclerotinia sclerotiorum, Microsphaera diffusa, Septoria glycine, Peronospora manshurica or Diaporthe caulivora (D. phaseolorum var. Caulivora), in each case on soybeans and genetically modified soybeans, for example Bt soybeans.
Crops of useful plants in which the compositions comprising the polymorph of the present invention disclosed herein can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
The term "useful plants" is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a Cryll IB(b1 ) toxin); Starlink* (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N- acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT* (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a Cry 11 IA toxin); Nature- Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.
Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola. Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include 8- endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.
An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
The fungicidal compositions comprising the polymorphs as disclosed herein as active ingredients, may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on transgenic soybean plants. In particular, transgenic soybean plants expressing toxins, for example insecticidal proteins such as delta-endotoxins, e.g. CrylAc (CrylAc Bt protein). Accordingly, this may include transgenic soybean plants comprising event MON87701 (disclosed in W02009/064652, as well as WO2014/170327 (eg, see paragraph [008] reference to Intacta RR2 PRO® soybean)), event MON87751 (disclosed in WO2014/201235) or event DAS-81419-2 (aka Conkesta™ Soybean, described in WO2013016527).
Useful transgenic events in transgenic soybean plants, which can be treated according to the invention, include event DAS-44406-6/pDAB8264.44.06.1 (soybean, herbicide-tolerance, disclosed in WO2012/075426); event DAS-81419-2 (aka Conkesta™ Soybean, described in WO2013016527 (aka Conkesta™ Enlist E3™ Soybean, DAS-81419-2 x DAS-44406-6); event DAS-14536- 7/pDAB8291 .45.36.2 (soybean, herbicide-tolerance, disclosed in WO2012/075429); DAS-68416-4 (soybean, herbicide-tolerance, ATCC Accession No. PTA-10442, disclosed in WO201 1/066384, WO201 1/066360); event DP-305423-1 (soybean, quality mark, disclosed in W02008/054747); event DP-356043-5 (soybean, herbicide-tolerance, deposited as ATCC PTA-8287, disclosed in W02008/002872); event FG72 (soybean, herbicide-tolerance, disclosed in WO201 1/063413); event LL27 (soybean, herbicide-tolerance, disclosed in W02006/108674); event LL55 (soybean, herbicidetolerance, disclosed in WO 2006/108675); event EE-GM3/FG72 (soybean, herbicide-tolerance) optionally stacked with event EE-GM1/LL27 or event EE-GM2/LL55 (disclosed in WO201 1/063413); event MON87701 (soybean, insect control, disclosed in W02009/064652, WO2014/170327); event MON87705 (soybean, improved fatty acid profile, herbicide-tolerance, disclosed in WO2010/037016); event MON87751 (lepidopteran-resistant, ATCC accession no. PTA-120166. disclosed in WO2014/201235); event MON87708 (soybean, herbicide-tolerance, disclosed in WO2011/034704); event MON87712 (soybean, yield, disclosed in WO2012/051 199); event MON87754 (soybean, quality feature, disclosed in WO2010/024976); event MON87769 (soybean, quality attribute, disclosed in W02009/102873); event MON89788 (soybean, herbicide-tolerance, disclosed in W02006/130436); event SYHT0H2/SYN-000H2-5 (soybean, herbicide-tolerance, disclosed in WO2012/082548); event DAS-21606-3 (soybean, herbicide-tolerance, disclosed in WO2012/033794); event 8264.44.06.1 (soybean, stacked herbicide-tolerance, disclosed in W02022/012075426); event pDAB8291 .45.36.2 (soybean, stacked herbicide-tolerance, disclosed in WO2012/075429); event pDAB8264.42.32.1 (soybean, stacked herbicide-tolerance, disclosed in WO2013/010094); event A2704-12 (glufosinate tolerance, disclosed in W02006/108647); event A5547-127 (phosphinothricin tolerant, disclosed in W02006/108675); event BPS-CV127- 91 (herbicide tolerance, disclosed in WO 2010/080829); event GU262 (phosphinothricin tolerant, described in APHIS regulatory reference US 98-238-01 p);
Particularly useful transgenic events in transgenic soybean plants, which can preferably be treated according to the invention, include event A2704-12 (glufosinate tolerance, disclosed in W02006/108647), event A5547-127 (phosphinothricin tolerant, disclosed in W02006/108675); event GU262 (phosphinothricin tolerant, described in APHIS regulatory reference US 98-238-01 p); event MON89788 (disclosed in W02006/130494A; event DP-305423-1 (soybean, quality mark, disclosed in W02008/054747); event MON87701 (soybean, insect resistant, disclosed in W02009/064652); event MON87705 (soybean, improved fatty acid profile, herbicide-tolerance, disclosed in WO2010/037016 or US20100080887A); event MON87769 (soybean, quality attribute, disclosed in W02009/102873 or US20110067141A); event FG72 (soybean, herbicide-tolerance, disclosed in WO2011/063413); event MON87712 (soybean, yield, disclosed in WO2012/051199); event BPS- CV127-9 (soybean, herbicide tolerance, deposited as NCIMB No. 41603, disclosed in WO2010/08082); event DAS-68416-4 (soybean, herbicide-tolerance, ATCC Accession No. PTA-10442, disclosed in WO2011/066384, WO2011/066360); event SYHT0H2/SYN-000H2-5 (soybean, herbicide-tolerance, disclosed in WO2012/082548); event DAS-44406-6/pDAB8264.44.06.1 (soybean, herbicide-tolerance, disclosed in WO2012/075426); event MON87751 (lepidopteran-resistant, ATCC accession no. PTA- 120166. disclosed in WO2014/201235); event MON87708 (soybean, herbicide-tolerance, disclosed in WO2011/034704) and event GMB151 (also called BCS-GM151-6, HPPD tolerance, disclosed in WO2018119364A1).
Furthermore, such a list of transgenic events is provided by the United States Department of Agriculture's (USDA) Animal and Plant Health Inspection Service (APHIS) and can be found on their website on the World Wide Web at aphis.usda.gov.
The term “event” as used herein refers to the event name that relates to a unique DNA recombination event that took place in one plant cell and which was then used to generate an entire transgenic plant. Detailed information on the events and associated products can be found on http://www.isaaa.org/gmapprovaldatabase. The events listed herein have been introduced into plants that are now commercially available.
Commercially available examples of transgenic soybeans, which can preferably be treated in a method according to the invention, include commercially available products such as plant seeds, which are under the ROUNDUP READY 2 XTEN®, INTACTA RR2 PRO®, VISTIVE® GOLD, Conkesta E3®, Conkesta Enlist E3™, LibertyLink® and/or Xtend Flex® trade names are sold or distributed.
Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704- 21 , A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
According to one embodiment of the invention, there is provided the use of a polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, for controlling phytopathogenic fungi in genetically modified soybean plants, wherein said Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21 , A5547- 127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
According to one embodiment of the invention, there is provided the use of a polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, for controlling phytopathogenic fungi in genetically modified soybean plants, wherein said Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21 , A5547- 127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127. According to one embodiment of the invention, there is provided the use of a polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, for controlling phytopathogenic fungi in genetically modified soybean plants, wherein said Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21 , A5547- 127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
The fungicidal polymorphs and compositions as disclosed herein may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soybean plants. In particular, there are known in the scientific literature certain Elite soybean plant varieties where R-gene stacks, conferring a degree of immunity or resistance to specific Phakopsora pachyrhizi, have been been introgressed in the plant genome, see for example: “Fighting Asian Soybean Rust’, Langenbach C, et al, Front Plant Science 7(797) 2016).
An elite plant is any plant from an elite line, such that an elite plant is a representative plant from an elite variety. Non-limiting examples of elite soybean varieties that are commercially available to farmers or soybean breeders include: AG00802, A0868, AG0902, A1923, AG2403, A2824, A3704, A4324, A5404, AG5903, AG6202 AG0934; AG1435; AG2031 ; AG2035; AG2433; AG2733; AG2933; AG3334; AG3832; AG4135; AG4632; AG4934; AG5831 ; AG6534; and AG7231 (Asgrow Seeds, Des Moines, Iowa, USA); BPR0144RR, BPR 4077NRR and BPR 4390NRR (Bio Plant Research, Camp Point, III., USA); DKB17- 51 and DKB37-51 (DeKalb Genetics, DeKalb, III., USA); DP 4546 RR, and DP 7870 RR (Delta & Pine Land Company, Lubbock, Tex., USA); JG 03R501 , JG 32R606C ADD and JG 55R503C (JGL Inc., Greencastle, Ind., USA); NKS 13-K2 (NK Division of Syngenta Seeds, Golden Valley, Minnesota, USA); 90M01 , 91 M30, 92M33, 93M11 , 94M30, 95M30, 97B52, P008T22R2; P16T17R2; P22T69R; P25T51 R; P34T07R2; P35T58R; P39T67R; P47T36R; P46T21 R; and P56T03R2 (Pioneer Hi-Bred International, Johnston, Iowa, USA); SG4771 NRR and SG5161 NRR/STS (Soygenetics, LLC, Lafayette, Ind., USA); S00-K5, S11-L2, S28-Y2, S43-B1 , S53-A1 , S76-L9, S78-G6, S0009-M2; S007-Y4; S04-D3; S14-A6; S20-T6; S21-M7; S26-P3; S28-N6; S30-V6; S35-C3; S36-Y6; S39-C4; S47-K5; S48-D9; S52-Y2; S58- Z4; S67-R6; S73-S8; and S78-G6 (Syngenta Seeds, Henderson, Ky., USA); Richer (Northstar Seed Ltd. Alberta, CA); 14RD62 (Stine Seed Co. la., USA); or Armor 4744 (Armor Seed, LLC, Ar., USA).
Thus, in a further preferred embodiment, fungicidal polymorphs and compositions as disclosed herein, are used to control Phakopsora pachyrhizi, (including fungicidally-resistant strains thereof, as outlined below) on Elite soybean plant varieties where R-gene stacks, conferring a degree of immunity or resistance to specific Phakopsora pachyrhizi, have been been introgressed in the plant genome. Numerous benefits may be expected to ensue from said use, e.g. improved biological activity, an advantageous or broader spectrum of activity (inc. sensitive and resistant strains of Phakopsora pachyrhizi), an increased safety profile, improved crop tolerance, synergistic interactions or potentiating properties, improved onset of action or a longer lasting residual activity, a reduction in the number of applications and/or a reduction in the application rate of the compounds and compositions required for effective control of the phytopathogen (Phakopsora pachyrhizi), thereby enabling beneficial resistancemanagement practices, reduced environmental impact and reduced operator exposure. Under certain circumstances, fungicidal compositions comprising the polymorphs according to the present invention and at least one additional active ingredient, when used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi (such as Phakopsora pachyrhizi) on soy bean plants (in particular any of the transgenic soybean plants as described above), may display a synergistic interaction between the active ingredients.
Exemplary GM traits that confer enhanced ASR resistance comprise resistance genes encoding resistance proteins as set forth in: W02019103918 (for example, but not limited to, RG-1 (SEQ ID NO: 47) and active variants or fragments thereof; or R-genes as set forth at SEQ ID NO: 28, 42, 43, 44, 45 or 46 ofW02019103918); WO202100878 (for example Rpp6907 (SEQ ID NO: 1 of WO202100878) and active variants or fragments thereof); WO2021022022 (for example, TirA or Tir B (SEQ ID NOS: 11 or 16 of WO2021022022, respectively) or active variants or fragments thereof); WO2021260673 (for example, but not limited to, RG21 and/or RG22 (SEQ ID NOS: 1 or 12 of WO2021260673) or active variants or fragments thereof); WO2022173659 (for example, but not limited to, RG30 (SEQ ID NO: 5 of WO2022173659) or active variants or fragments thereof); WO2022159341 (for example but not limited to SEQ ID NOS: 1 and 148 of WO2022159341 or active variants or fragments thereof); WO2021154632A1 , WO2021022026, W02021022101 , US20220135997 (for example, but not limited to, FIT1 (SEQ ID NO: 2 of US20220135997), an active variant or fragment thereof or any of the FIT1 paralogs or orthologs disclosed therein (such as SEQ ID NOS: 4, 6, 8, 10, 12, 14, 16, 18 or 20 of US20220135997); US10842097 (for example, but not limited to, CcRppI or active variants or fragments thereof or any other resistance genes disclosed therein); WO2022140257 (for example, CcRpp2-R1 and/or CcRpp2-R3 (SEQ ID NOS: 2 or 4 of WO2022140257) or an active variant or fragment thereof); the resistance genes disclosed in US Provisional Application NO. 63/481627 as RG31 (SEQ ID NOS:
1 , 3, or 4) or RG35 (SEQ ID NOS: 2 or 5); and/or the resistance genes disclosed in US Provisional Application Nos. 63/426524 and 63/509586 as RG32 (SEQ ID NOS: 1 , 3, or 4) or RG34 (SEQ ID NOS:
2, 5, 6, or 17); each of which is incorporated by reference in their entirety.
Exemplary native traits that confer increased resistance to ASR or to pathogens from the genus Phakopsora, including the species Phakopsora pachyrhizi and Phakopsora meibomiae include various intervals and locus (loci) associated with Rpp1 , Rppl b, Rpp2, Rpp4, Rpp5, Rpp6 and ASR resistance locus 1-16. Such native traits can be found, for example, in W02009079729, US8759607, US8962914, W02008054546, US8692054, US9091681 , W02009132089, US8669414, US8796503, US8921645, WO2010096227, WO2010009404, WQ2021154632, US20230067451 , WQ2021022026, US20220256795, WQ2021022101 , US20220338433A1 , WQ2022173659, WQ2010009404, WQ2017222827, US20210024950, WQ2021000878, US20220380796, US20230147114, and PCT App. No. PCT/US23/60373, each of which is incorporated by reference in their entirety.
Exemplary Soybean varieties that confer increased resistance to ASR include soybean cultivars TMG 7062, TMG 7161 and TMG 7261 .
Further Soybean varieties that confer increased resistance against ASR (caused by Phakopsora pachyrhizi) inlcude for example, but not limited to TMG7368 IPRO (Disclosed in WQ2009079729), TMG7062 IPRO, TMG 7063 IPRO, and TMG 7061 IPRO. Further Soybean varieties that confer increased resistance against ASR (caused by Phakopsora pachyrhizi) inlcude for example, but not limited to soybeans with Shield Technology, like for example BRS511 soybean, BRS 531 soybean, or Soy-BRS 539 (conventional soybean with Shield® and Block® Technologies).
Fungicidal-resistant strains of Phakopsora pachyrhizi have been reported in the scientific literature, with strains resistant to one or more fungicides from at least each of the following fungicidal mode of action classes being observed: sterol demethylation-inhibitors (DMI), quinone-outside-inhibitors (Qol) and succinate dehydrogenase inhibitors (SDHI). See for example: “Sensitivity of Phakopsora pachyrhizi towards quinone-outside-inhibitors and demethylation-inhibitors, and corresponding resistance mechanisms.” Schmitz HK et al, Pest Manag Sci (2014) 70: 378-388; “First detection of a SDH variant with reduced SDHI sensitivity in Phakopsora pachyrhizi’ Simoes K et al, J Plant Dis Prot (2018) 125: 21-2; “Compef/f/ve fitness of Phakopsora pachyrhizi isolates with mutations in the CYP51 and CYTB genes.” Klosowski AC et al, Phytopathology (2016) 106: 1278-1284; “Detection of the F129L mutation in the cytochrome b gene in Phakopsora pachyrhizi." Klosowski AC et al, Pest Manag Sci (2016) 72: 1211-1215.
In another embodiment of the invention, there is provided a method of controlling or preventing infestation of genetically modified plants by phytopathogenic microorganisms, especially phytopathogenic fungi, wherein a crystalline polymorph (form A) of the compound methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to said plants. Preferably the genetically modified plants are soybean plants. Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), lntacta®2 Xtend™, Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™. More preferably the genetically modified plants are Bt soybean plants. Examples of “Bt plants” are for example soybean varieties which are sold under the trade names Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™. Even more preferably, the Bt soybean plants are selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
In another embodiment of the invention, there is provided a method of controlling or preventing infestation of genetically modified plants by phytopathogenic microorganisms, especially phytopathogenic fungi, wherein a crystalline polymorph (form B) of the compound methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to said plants. Preferably the genetically modified plants are soybean plants. Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), lntacta®2 Xtend™, Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™. More preferably the genetically modified plants are Bt soybean plants. Examples of “Bt plants” are for example soybean varieties which are sold under the trade names Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™. Even more preferably, the Bt soybean plants are selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
In another embodiment of the invention, there is provided a method of controlling or preventing infestation of genetically modified plants by phytopathogenic microorganisms, especially phytopathogenic fungi, wherein a crystalline polymorph (form C) of the compound methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein is applied to said plants. Preferably the genetically modified plants are soybean plants. Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), lntacta®2 Xtend™, Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™. More preferably the genetically modified plants are Bt soybean plants. Examples of “Bt plants” are for example soybean varieties which are sold under the trade names Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™. Even more preferably, the Bt soybean plants are selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
In a preferred embodiment of the invention, there is provided a method for controlling pests on soybean plants, wherein said soybean plants are Bt soybean plants, preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®, characterized by comprising the step of contacting the plant, parts thereof, propagation material thereof, the pests, their food source, habitat, or breeding ground with a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate.
In another preferred embodiment of the invention, there is provided a method for controlling pests on soybean plants, wherein said soybean plants are Bt soybean plants, preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®, characterized by comprising the step of contacting the plant, parts thereof, propagation material thereof, the pests, their food source, habitat, or breeding ground with a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2- methyl-phenoxy)-3-methoxy-prop-2-enoate.
In another preferred embodiment of the invention, there is provided a method for controlling pests on soybean plants, wherein said soybean plants are Bt soybean plants, preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®, characterized by comprising the step of contacting the plant, parts thereof, propagation material thereof, the pests, their food source, habitat, or breeding ground with a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2- methyl-phenoxy)-3-methoxy-prop-2-enoate.
Commercially available examples of genetically modified soybean plants, which can preferably be treated according to the invention, include commercially available products such as plant seeds, which are under the Intacta®, lntacta®2, lntacta®2 Xtend™, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, or Plenish™ trade names are sold or distributed.
Commercially available examples of Bt soybean plants, which can preferably be treated according to the invention, include commercially available products such as plant seeds, which are sold under the trade names Intacta®, lntacta®2, lntacta®2 Xtend™, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, or Plenish™.
Preferably genetically modified soybean plants, which can be treated according to the invention, are selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
In another embodiment of the invention, there is provided the use of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, for controlling phytopathogenic fungi (preferably, phakopsora pachyrhizi) in genetically modified plants. Preferably the genetically modified plants are soybean plants. More preferably said genetically modified soybean plants are Bt soybean plants, even more preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
In another embodiment of the invention, there is provided the use of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, for controlling phytopathogenic fungi (preferably, phakopsora pachyrhizi) in genetically modified plants. Preferably the genetically modified plants are soybean plants. More preferably said genetically modified soybean plants are Bt soybean plants, even more preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
In another embodiment of the invention, there is provided the use of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, for controlling phytopathogenic fungi (preferably, phakopsora pachyrhizi) in genetically modified plants. Preferably the genetically modified plants are soybean plants. More preferably said genetically modified soybean plants are Bt soybean plants, even more preferably Bt soybean plants selected from Intacta RR2 PRO®, or Conkesta Enlist E3®.
As used herein, the term “genetically modified plant” or “genetically modified soybean plant” refers to a plant or soybean plant, in which the genetic material has been altered in a way that does not occur naturally by mating and /or natural recombination. These plants are also called transgenic or genetically engineered plants. Genetic modification of plants involves adding a specific stretch of DNA into the plant’s genome, giving it new or different characteristics. This could include changing the way the plant grows or making it resistant to a particular disease. Examples of genetically modified soybean plants are available under the tradenames YIELD GARD®, Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™.
As used herein, the term “Bt soybean plant” refers to soybean plants that are genetically engineered soybeans that produce an insecticidal protein like the one naturally produced by the bacteria species Bacillus thuringiensis, for example by the genes CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, Cry II IB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and also combinations thereof. These soybeans that are genetically engineered to produce the same toxin as Bacillus thuringiensis (Bt) in every cell of the plant, with the goal of protecting the soybean from pests, are referred to herein as "Bt soybeans”. Examples Bt soybean plants are Intacta RR2 PRO®, or Conkesta Enlist E3®.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g., in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating, or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
Suitable carriers and adjuvants, e.g., for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g. e.g., natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 1997/33890.
Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.
Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours, and other organic and inorganic solids which act as dispersants and carriers.
The active ingredients (polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5- cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein) and mixtures thereof with component (B) and/or (C)) can also be contained in micro-'capsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g., slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane, or chemically modified polymers, and starch xanthates, or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdustsawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein the active ingredient is dispersed in finely divided form as a result ofbecause of vaporisation of a low boiling dispersant solvent carrier, may also be used.
Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to a person skilled in the art.
Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 ,1 ,1-trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates.
Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.
A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.
In addition, further, other biocidal active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.
In addition, the compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g., fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non- selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient a polymorph as defined herein, in free form or in agrochemical usable salt form, and at least one of the above-mentioned adjuvants.
The invention therefore provides a composition, preferably a fungicidal composition, comprising a polymorph (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, an agriculturally acceptable carrier and optionally an adjuvant. An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, said composition may comprise at least one or more pesticidal-active compounds, for example an additional fungicidal active ingredient in addition to the polymorph (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2- methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein.
The polymorphs (form A, or form B, or form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide, or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities.
Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorous fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.
Examples of suitable additional active ingredients include the following: petroleum oils, 1 ,1-bis(4- chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1- naphthylacetamide, 4-chlorophenyl phenyl sulfone, acetoprole, aldoxycarb, amidithion, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenous oxide, azobenzene, azothoate, benomyl, benoxa-fos, benzyl benzoate, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbanolate, carbophenothion, cymiazole, chinomethionat, chlorbenside, chlordimeform, chlordimeform hydrochloride, chlorfenethol, chlorfenson, chlorfensulfide, chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate, chlorthiophos, cinerin I, cinerin II, cinerins, closantel, coumaphos, crotamiton, crotoxyphos, cufraneb, cyanthoate, DCPM, DDT, demephion, demephion-O, demephion-S, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S- methylsulfon, dichlofluanid, dichlorvos, dicliphos, dienochlor, dimefox, dinex, dinex-diclexine, dinocap- 4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, dioxathion, diphenyl sulfone, disulfiram, DNOC, dofenapyn, doramectin, endothion, eprinomectin, ethoate-methyl, etrimfos, fenazaflor, fenbutatin oxide, fenothiocarb, fenpyrad, fenpyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine, flucycloxuron, fluenetil, fluorbenside, FMC 1137, formetanate, formetanate hydrochloride, formparanate, gamma-HCH, glyodin, halfenprox, hexadecyl cyclopropanecarboxylate, isocarbophos, jasmolin I, jasmolin II, jodfenphos, lindane, malonoben, mecarbam, mephosfolan, mesulfen, methacrifos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3- pyridyl)methoxy]pyridazin-3-one, nifluridide, nikkomycins, nitrilacarb, nitrilacarb 1 :1 zinc chloride complex, omethoate, oxydeprofos, oxydisulfoton, pp'-DDT, parathion, permethrin, phenkapton, phosalone, phosfolan, phosphamidon, polychloroterpenes, polynactins, proclonol, promacyl, propoxur, prothidathion, prothoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pyrimitate, quinalphos, quintiofos, R-1492, phosglycin, rotenone, schradan, sebufos, selamectin, sophamide, SSI-121 , sulfiram, sulfluramid, sulfotep, sulfur, diflovidazin, tau-fluvalinate, TEPP, terbam, tetradifon, tetrasul, thiafenox, thiocarboxime, thiofanox, thiometon, thioquinox, thuringiensin, triamiphos, triarathene, triazophos, triazuron, trifenofos, trinactin, vamidothion, vaniliprole, bethoxazin, copper dioctanoate, copper sulfate, cybutryne, dichlone, dichlorophen, endothal, fentin, hydrated lime, nabam, quinoclamine, quinonamid, simazine, triphenyltin acetate, triphenyltin hydroxide, crufomate, piperazine, thiophanate, chloralose, fenthion, pyridin-4-amine, strychnine, 1 -hydroxy-1 H-pyridine-2-thione, 4-(quinoxalin-2- ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodicin, fenaminosulf, formaldehyde, hydrargaphen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate, probenazole, streptomycin, streptomycin sesquisulfate, tecloftalam, thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid, penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate, (E)-6- methylhept-2-en-4-ol, (E,Z)-tetradeca-4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec- 11-enal, (Z)-hexadec-l 1-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-icos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodeca-7,9-dien- 1-yl acetate, (9Z,11 E)-tetradeca-9,11-dien-1-yl acetate, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate, 14- methyloctadec-1-ene, 4-methylnonan-5-ol with 4-methylnonan-5-one, alpha-multistriatin, brevicomin, codlelure, codlemone, cuelure, disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodeca-8, 10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, frontalin, grandlure, grandlure I, grandlure II, grandlure III, grandlure IV, hexalure, ipsdienol, ipsenol, japonilure, lineatin, litlure, looplure, medlure, megatomoic acid, methyl eugenol, muscalure, octadeca-2,13-dien-1-yl acetate, octadeca- 3, 13-dien-1 -yl acetate, orfralure, oryctalure, ostramone, siglure, sordidin, sulcatol, tetradec-11-en-1-yl acetate, trimedlure, trimedlure A, trimedlure B1 , trimedlure B2, trimedlure C, trunc-call, 2- (octylthio)ethanol, butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyltoluamide, dimethyl carbate, dimethyl phthalate, ethyl hexanediol, hexamide, methoquin-butyl, methylneodecanamide, oxamate, picaridin, 1-dichloro-1 -nitroethane, 1 ,1-dichloro-2,2- bis(4-ethylphenyl)ethane, 1 ,2-dichloropropane with 1 ,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2- (4,5-dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2-isovalerylindan-1 ,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1 -chloroprop-1 -ene, 3-methyl-1-phenylpyrazol- 5-yl dimethylcarbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate, 5,5-dimethyl-3- oxocyclohex-1-enyl dimethylcarbamate, acethion, acrylonitrile, aldrin, allosamidin, allyxycarb, alphaecdysone, aluminium phosphide, aminocarb, anabasine, athidathion, azamethiphos, Bacillus thuringiensis delta endotoxins, barium hexafluorosilicate, barium polysulfide, barthrin, Bayer 22/190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromfenvinfos, bromo-DDT, bufencarb, butacarb, butathiofos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, cevadine, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxim, chlorprazophos, cis-resmethrin, cismethrin, clocythrin, copper acetoarsenite, copper arsenate, copper oleate, coumithoate, cryolite, CS 708, cyanofenphos, cyanophos, cyclethrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidafos, dicapthon, dichlofenthion, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dilor, dimefluthrin, dimetan, dimethrin, dimethylvinphos, dimetilan, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzofos, dithicrofos, DSP, ecdysterone, El 1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenchlorphos, fenethacarb, fenitrothion, fenoxacrim, fenpirithrin, fensulfothion, fenthion-ethyl, flucofuron, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, guazatine, guazatine acetates, sodium tetrathiocarbonate, halfenprox, HCH, HEOD, heptachlor, heterophos, HHDN, hydrogen cyanide, hyquincarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isolane, isoprothiolane, isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lead arsenate, leptophos, lirimfos, lythidathion, m- cumenyl methylcarbamate, magnesium phosphide, mazidox, mecarphon, menazon, mercurous chloride, mesulfenfos, metam, metam-potassium, metam-sodium, methanesulfonyl fluoride, methocrotophos, methoprene, methothrin, methoxychlor, methyl isothiocyanate, methylchloroform, methylene chloride, metoxadiazone, mirex, naftalofos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, 0-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate, O,O-diethyl 0-4- methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl 0-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, O,O,O',O'-tetrapropyl dithiopyrophosphate, oleic acid, para-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, phenkapton, phosnichlor, phosphine, phoxim-methyl, pirimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, prothiofos, pyrazophos, pyresmethrin, quassia, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, kadethrin, ryania, ryanodine, sabadilla, schradan, sebufos, SI-0009, thiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenoxide, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, sulprofos, tar oils, tazimcarb, TDE, tebupirimfos, temephos, terallethrin, tetrachloroethane, thicrofos, thiocyclam, thiocyclam hydrogen oxalate, thionazin, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormetaphos-3, trichloronat, trimethacarb, tolprocarb, triclopyricarb, triprene, veratridine, veratrine, XMC, zetamethrin, zinc phosphide, zolaprofos, meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, pyrimorph, trifenmorph, 1 ,2-dibromo-3-chloropropane, 1 ,3-dichloropropene, 3,4- dichlorotetrahydrothiophene 1 ,1 -dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo- 1 ,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, anisiflupurin, benclothiaz, cytokinins, DCIP, furfural, isamidofos, kinetin, Myrothecium verrucaria composition, tetrachlorothiophene, xylenols, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin, antu, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropadine, flupropadine hydrochloride, norbormide, phosacetim, phosphorus, pindone, pyrinuron, scilliroside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonylate, 5-(1 ,3-benzodioxol-5-yl)- 3-hexylcyclohex-2-enone, farnesol with nerolidol, verbutin, MGK 264, piperonyl butoxide, piprotal, propyl isomer, S421 , sesamex, sesasmolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, sulphur, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, chloroinconazide, mercuric oxide, thiophanate-methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazole, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethirimol, ethirimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, chlozolinate, dichlozoline, myclozoline, procymidone, vinclozoline, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, folpet, tolylfluanid, bordeaux mixture, copper oxide, mancopper, oxine-copper, nitrothal-isopropyl, edifenphos, iprobenphos, phosdiphen, tolclofos-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, cyclobutrifluram, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim.fluopicolide, fluoxytioconazole, flusulfamide, fluxapyroxad, fenhexamid, fosetylaluminium, hymexazol, iprovalicarb, cyazofamid, methasulfocarb, metrafenone, pencycuron, phthalide, polyoxins, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriofenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, triforine, validamycin, valifenalate, zoxamide, mandipropamid, flubeneteram, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 2,4-D (2,4- dichlorophenoxyacetic acid), 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro- biphenyl-2-yl)-amide, isoflucypram, isotianil, dipymetitrone, 6-ethyl-5,7-dioxo- pyrrolo[4,5][1 ,4]dithiino[1 ,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1 ,1-dimethyl- indan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4- fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4- (2- bromo- 4- fluorophenyl) - N- (2- chloro- 6- fluorophenyl) - 1 , 3- dimethyl- 1 H- pyrazol- 5- amine, fluindapyr, coumethoxystrobin (jiaxiangjunzhi), Ivbenmixianan, dichlobentiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3- dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiprolin, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2- pyridyl]carbamate, pyraziflumid, inpyrfluxam, trolprocarb, mefentrifluconazole, ipfentrifluconazole, 2- (difluoromethyl)-N-[(3R)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4- phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl- phenyl]-N-ethyl-N-methyl-formamidine, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4- piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate, but-3-ynyl N-[6- [[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl N-[[5-[4- (2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4- (2,4,6-trifluorophenyl)pyridazine, pyridachlometyl, 3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan- 4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4- methyl-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1- yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, ametoctradin, amisulbrom, penflufen, (Z,2E)-5- [1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide, florylpicoxamid, fenpicoxamid, metarylpicoxamid, tebufloquin, ipflufenoquin, quinofumelin, isofetamid, ethyl 1-[[4-[[2- (trifluoromethyl)-l ,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020/056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1- enoxy]phenyl]methyl]pyrazole-3-carboxylate (may be prepared from the methods described in WO 2020/056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl- phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (may be prepared from the methods described in WO 2020/097012), 6-chloro-3-(3-cyclopropyl-2-fluoro- phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)- 2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391), 6-chloro-3-(3-cyclopropyl-2-fluoro- phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (may be prepared from the methods described in WO 2020/109391), N-[2-[2, 4-dichloro-phenoxy]phenyl]-3- (difluoromethyl)-1-methyl-pyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]- 3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, benzothiostrobin, phenamacril, 5-amino-1 ,3,4- thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoyne, picarbutrazox, 2-(difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, 2- (difluoromethyl)-N-((3R)-1 ,1 ,3-trimethylindan-4-yl) pyridine-3- carboxamide, 4-[[6-[2-(2,4- difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, metyltetraprole, a-(1 ,1-dimethylethyl)-a-[4'-(trifluoromethoxy) [1 ,1 '- biphenyl]-4-yl]-5- pyrimidinemethanol, fluoxapiprolin, enoxastrobin, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3- (1 , 2 ,4-tri azo I- 1 -yl)propyl]-3-pyridyl]oxy] benzonitrile, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy- 3-(1 ,2,4-triazol-1-yl)propanoate, methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1 ,2,4-triazol-
1-ylmethyl)cyclopentanecarboxylate, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(5-sulfanyl- 1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy] benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-
3-(5-thioxo-4H-1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac-ethyl, coumoxystrobin, zhongshengmycin, thiodiazole copper, zinc thiazole, amectotractin, iprodione, seboctylamine, thiamethoxam, N'-[5-bromo-2-methyl-6-[(1 S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl- formamidine, N'-[5-bromo-2-methyl-6-[(1 R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl- formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl- formamidine (these compounds may be prepared from the methods described in WO2015/155075); N'- [5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in IPCOM000249876D); N-isopropyl-N’-[5-methoxy-2-methyl-
4-(2, 2, 2-trifl u o ro- 1 -hydroxy-1 -phenyl-ethyl)phenyl]-N-methyl-formamidine, N’-[4-(1 -cyclopropyl-2,2,2- trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds may be prepared from the methods described in WO 2018/228896); N-ethyl-N’-[5-methoxy-
2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N’-[5-methoxy-2- methyl-4-[(2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds may be prepared from the methods described in WO2019/110427); N-[(1 R)-1-benzyl-3-chloro-1-methyl-but-
3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro- quinoline-3-carboxamide, N-[(1 R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3- carboxamide, N-[(1 S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N- [(1 R)-1 -benzyl- 1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1 S)-1 -benzyl- 1 ,3- dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1 R)-1 -[(3-fluorophenyl)methyl]-1 ,3- dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1 S)-1 -[(3-fluorophenyl)methyl]-1 ,3-dimethyl- butyl]quinoline-3-carboxamide, N-[(1 R)-1 -benzyl- 1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 S)-1 -benzyl- 1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1 R)-1 -benzyl-3-chloro-1 - methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1 S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)- 8-fluoro-quinoline-3-carboxamide (these compounds may be prepared from the methods described in WO2017/153380); 1 -(6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline,
1-(6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3- dimethyl-1 -(6-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1 -(7- methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline, 1 -(6-chloro-7-methyl-pyrazolo[1 ,5-a]pyridin-3-yl)-4,4- difluoro-3,3-dimethyl-isoquinoline (these compounds may be prepared from the methods described in WO2017/025510); 1 -(4,5-dimethylbenzimidazol-1 -yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1 -(4,5- dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1- (4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3- dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H- cyclopenta[e]benzimidazole (these compounds may be prepared from the methods described in WO2016/156085), N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide, 1 -methoxy-3-methyl-1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl] methyl]urea, 1 ,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea,
3-ethy I- 1 -methoxy-1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-
(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-
(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-
(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, ethyl 1 -[[4-[5-(trifluoromethyl)-
1 .2.4-oxadiazol-3-yl]phenyl] methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-
1 .2.4-oxadiazol-3-yl]phenyl]methyl]-1 ,2,4-triazol-3-amine (these compounds may be prepared from the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689);
2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO2017/029179); 2-[6-(4-bromophenoxy)-2- (trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy- propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO2016/156290); 3-[2-(1 -chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-
4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290); (4- phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound may be prepared from the methods described in WO2014/006945); 2,6-Dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole- 1 ,3,5,7(2H,6H)-tetrone (this compound may be prepared from the methods described in WO2011/138281) N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzenecarbothioamide; N- methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol- 3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO2018/153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl- formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound may be prepared from the methods described in WO 2016/202742); 2-(difluoromethyl)-N- [(3S)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO2014/095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methanone (these compounds may be prepared from the methods described in WO2017/220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO2018/065414); ethyl 1-[[5-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO2018/158365); 2,2-difluoro-N-methyl-2-[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-
(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]benzamide (these compounds may be prepared from the methods described in WO 2018/202428); 1-[1-(4-chloro phenyl)cyclobutyl]ethyl (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl)-amino]propanoate; [2-(4-bromo-7-fluoro-indol-1 -yl)-1 -methyl-propyl] (2S)-2-[(3-hydroxy-4- methoxy-pyridine-2-carbonyl) amino]propanoate; [2-(3,5-dichloro-2-pyridyl)-1 -methyl-propyl] (2S)-2-[(3- hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate; [(1 S)-1 -[1 -(1 -naphthyl)cyclopropyl]ethyl] (2S)-2-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino] propanoate, [(1 S)-1 -[1 -(1 - naphthyl)cyclopropyl]ethyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate, [2- [[(1 S)-2-[2-(3,5-dichloro-2-pyridyl)-1 -methyl-propoxy]-1 -methyl-2-oxo-ethyl] carbamoyl]-4-methoxy-3- pyridyl]oxymethyl 2-methylpropanoate, [4-methoxy-2-[[(1 S)-1 -methyl-2-[(1 S)-1 -[1 -(1 - naphthyl)cyclopropyl]ethoxy]-2-oxo-ethyl]carbamoyl]-3-pyridyl]oxymethyl 2-methylpropanoate; [2-(4- bromophenyl)-1 ,2-dimethyl-propyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl)amino]propanoate; 1 -(1 -phenyl cyclohexyl)ethyl (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl)amino]propanoate; [1-methyl-2-(2-quinolyl)propyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2- carbonyl) amino]propanoate; [2-(7-bromoindol-1 -yl)-1 -methyl-propyl] (2S)-2-[(3-hydroxy-4-methoxy- pyridine-2-carbonyl) amino]propanoate; [1 -methyl-2-[6-(trifluoromethyl)indol-1 -y I] propyl] (2S)-2-[(3- hydroxy-4-methoxy-pyridine-2-carbonyl) amino]propanoate, (2-indazol-1 -yl-1 -methyl-propyl) (2S)-2-[(3- hydroxy-4-methoxy-pyridine-2-carbonyl) amino]propanoate, [2-(5-chloro-2-thienyl)-1 -methyl-propyl] (2S)-2-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl) amino]propanoate, [2-(4,7-dichloroindol-1 -yl)-1 - methyl-propyl] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]propanoate, [2-(7-bromo-4- fluoro-indol-1 -yl)-1 -methyl-propyl] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl) amino]propanoate, [(1 S)-1 -[1 -(1 -naphthyl)cyclopropyl]ethyl] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2- carbonyl)amino]propanoate (these compounds may be prepared from the methods described in W02020/208096); methyl N-[[5-[1 -(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl- phenyl]methyl]carbamate; methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl- phenyl]methyl]carbamate; (2E)-2-methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-1-[4-(trifluoromethyl)-2- pyridyl]ethylideneamino]oxymethyl]phenyl]acetamide; 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N- [2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide; 6-chloro-N-[2-(2-chloro- 4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4- carboxamide; 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro- ethyl]-5-methyl-pyridazine-4-carboxamide; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6- difluorophenyl)ethyl] pyrimidin-2-amine; 2-(difluoromethyl)-5-[2-[1-(2,6- difluorophenyl)cyclopropoxy]pyrimidin-5-yl]-1 ,3,4-oxadiazole; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2- yl]-N-[1-(2,6-difluorophenyl)cyclopropyl]pyrimidin-2-amine; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]- N-[1 -(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine; N-[1 -(2-fluorophenyl)cyclopropyl]-5-[5-
(trifluoromethyl)-l ,3,4-oxadiazol-2-yl]pyrimidin-2-amine; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N- [1-(2-fluorophenyl)ethyl] pyrimidin-2-amine; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(3,5- difluorophenyl)ethyl]pyrimidin-2-amine; ethyl 1 -[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2- yl]methoxy]phenyl]methyl]-1 H-pyrazole-4-carboxylate; ethyl 1 -[[4-[[(1 Z)-2-ethoxy-3,3,3-trifluoro-1 - propen-1 -yl]oxy]phenyl]methyl]-1 H-pyrazole-4-carboxylate; 3-[[3-chloro-2-(2-ethylpyrazol-3-yl)phenyl] methyl]-7,8-difluoro-2-methyl-quinoline; N-[2-(2-ethylpyrazol-3-yl)phenyl]-5,6-difluoro-3-methyl- quinoxalin-2-amine; 5,6-difluoro-N-[3-fluoro-2-(2-propylpyrazol-3-yl)phenyl]-3-methyl-quinoxalin-2- amine; N-[3-chloro-2-(2-propylpyrazol-3-yl)phenyl]-7,8-difluoro-2-methyl-quinolin-3-amine; 1-(5,6- dimethyl-3-pyridyl)-4,4-difluoro-3,3-dimethyl-isoquinoline; 1-[6-(difluoromethyl)-5-methyl-3-pyridyl]-4,4- difluoro-3,3-dimethyl-isoquinoline; Methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4- triazol-1 -yl)propanoate and 2-(1 -chlorocyclopropyl)-1 -(2-chlorophenyl)-3-(1 , 2 ,4-tri azo I- 1 -yl)propan-2-ol.
In a preferred embodiment suitable additional active ingredients are selected from the group consisting of benzovindiflupyr, fluxapyroxad, pydiflumetofen.isopyrazam, fluopyram, penthiopyrad, sedaxane, bixafen, difenoconazole, cyproconazole, tebuconazole, hexaconazole, prothioconazole, propiconazole, epoxiconazole, metconazole, tetraconazole, fluoxytioconazole, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]- 2-hydroxy-3-(1 , 2 ,4-tri azo I- 1 -yl)propanoate, methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy-1 -methyl-2- (1 ,2,4-triazol-1-ylmethyl)cyclopentanecarboxylate, flutriafol, mefentrifluconazole, ipconazole, paclobutrazol, azoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, metalaxyl-M, fenpropidin, fenpropimorph, cyprodinil, spiroxamine, mancozeb, chlorothalonil, folpet, copper-oxychloride, copperhydroxide, Sulphur, oxathiapiprolin, ipflufenoquin, quinofumelin, mandipropamid, fluazinam, fludioxinil, fosetyl-aluminium, acibenzolar-Smethyl, enestrobin, inpyrfluxam, fluindapyr, isoflucypram, metyltetraprole, florylpicoxamid, metarylpicoxamide, flefunoxadiazam isofetamid, procymidone, carbendazim, fenhexamid, prochloraz, prohexadione-calcium, melaluca alternifolia oil (an extract of the tea tree plant Melaluca alternifolia (commercially available as Timorex Gold®, which is a broad-spectrum botanical biofungicide)), N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N- methylformamidine, cyclobutrifluram calcium phosphonate, cis-jasmone, trinexapac-ethyl, glyphosate, 2,4-D (2,4-dichlorophenoxyacetic acid) and thiamethoxam.
The compounds of the invention may also be used in combination with anthelmintic agents. Such anthelmintic agents include, compounds selected from the macrocyclic lactone class of compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP-357460, EP-444964 and EP- 594291 . Additional anthelmintic agents include semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO-9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
The polymorphs of the invention may be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US- 4639771 and DE-19520936.
The polymorphs of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO9615121 and also with anthelmintic active cyclic depsipeptides such as those described in WO961 1945, WO9319053, WO 9325543, EP-626375, EP-382173, WO-9419334, EP-382173, and EP-503538.
The polymorphs of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
The polymorphs of the invention may be used in combination with terpene alkaloids, for example those described in WO95/19363 or W004/72086, particularly the compounds disclosed therein.
Other examples of such biologically active compounds that the compounds of the invention may be used in combination with include but are not restricted to the following:
Organophosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacriphos, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos- methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.
Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801 , isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.
Pyrethroids: acrinathin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1 R)-cis-2,2-dimethyl-3-(2- oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a- cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, Zeta-cypermethrin.
Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
Other antiparasitics: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, fenazaquin, flumite, MTI- 800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzine, flufenprox, fluproxyfen, halofenprox, hydramethylnon, I KI-220 , kanemite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651 , WL-108477, pirydaryl, propargite, protrifenbute, pymethrozine, pyridaben, pyrimidifen, NC-1111 , R-195.RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601 , silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, YI-5301 .
Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus, and fungi.
Bactericides: chlortetracycline, oxytetracycline, streptomycin.
Other biological agents: enrofloxacin, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfen icol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel, triclabendazole.
The following mixtures of the polymorphs with active ingredients are preferred, wherein TX represents a crystalline polymorph form A of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate, or a crystalline polymorph form B of the compound methyl (Z)-2-(5-cyclohexyl- 2-methyl-phenoxy)-3-methoxy-prop-2-enoate, or a crystalline polymorph form C of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate: a compound selected from the group of substances consisting of
(4E,10Z)-tetradeca-4, 10-dienyl acetate + TX; (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX; (E)-6- methylhept-2-en-4-ol + TX; (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX; (E)-tridec-4-en-1-yl acetate + TX; (S)-bioallethrin + TX; (Z)-dodec-7-en-1-yl acetate + TX; (Z)-hexadec-11-en-1-yl acetate + TX; (Z)-hexadec-11-enal + TX; (Z)-hexadec-13-en-11 -yn-1 -yl acetate + TX; (Z)-icos-13-en-10-one + TX; (Z)-tetradec-7-en-1-al + TX; (Z)-tetradec-9-en-1-ol + TX; (Z)-tetradec-9-en-1-yl acetate + TX; 1 ,1 -bis(4- chlorophenyl)-2-ethoxyethanol + TX; 1-(2-chlorophenyl)-3,3-dimethyl-2-(1 ,2,4-triazol-1-ylmethyl)butan- 2-ol + TX; 1-(5-bromo-2-pyridyl)-2-(2,4-difluorophenyl)-1 , 1 -difluoro-3-(1 ,2,4-triazol-1-yl)propan-2-ol + TX; 1 -hydroxy-1 H-pyridine-2-thione + TX; 1 -methylcyclopropene + TX; 1 -naphthaleneacetamide + TX;
1 -naphthylacetic acid + TX; 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX; 2,4-D + TX; 2,4-DB + TX; 2,6-dichloro-N-(4-trifluormethylbenzyl)benzamide + TX; 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX; 2-(2-butoxyethoxy)ethyl piperonylate + TX; 2-(4,5-dimethyl-1 ,3-dioxolan-2- yl)phenyl methylcarbamate + TX; 2-(difluoromethyl)-N-((3R)-1 ,1 ,3-trimethylindan-4-yl) pyridine-3- carboxamide + TX; 2-(octylthio)-ethanol + TX; 2-bromo-2-bromomethyl-pentanedinitrile + TX; 2- chlorovinyl diethyl phosphate + TX; 2-imidazolidone + TX; 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX; 2-thiocyanatoethyl laurate + TX; 3-(4-chlorophenyl)-5-methylrhodanine + TX; 3- (difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX; 3-(difluoromethyl)- N-(7-fluoro-1 ,1 ,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide + TX; 3-(difluoromethyl)- N-(7-fluoro-1 ,1 ,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide + TX; 3-chloro-6-methyl- 5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX; 3-methyl-1-phenylpyrazol-5-yl dimethyl-carbamate + TX; 3-phenylphenol + TX; 4,5-dichlorodithiol-3-one + TX; 4-(2,6-difluorophenyl)-6-methyl-5-phenyl- pyridazine-3-carbonitrile + TX; 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl- pyrazol-3-amine + TX; 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX; 4-[[6-[2-(2,4-difluorophenyl)- 1 ,1-difluoro-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX; 4-chloro-2-(2-chloro-
2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX; 4-CPA + TX; 4-methyl(prop-2- ynyl)amino-3,5-xylyl methylcarbamate + TX; 4-methylnonan-5-ol with 4-methylnonan-5-one + TX; 4- phenylphenol + TX; 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX; 5-amino-1 ,3,4-thiadiazole- 2-thiol + TX; 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine + TX; 5-hydroxy-6-methyl-4-(((E)-pyridin-3- ylmethylene)amino)-4,5-dihydro-1 ,2,4-triazin-3(2H)-one + TX; 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3- ylacetic acid + TX; 8-hydroxyquinoline sulfate + TX; 11 -ethyl- 10, 12-dioxo-2,5,8-trithia-4, 11 - diazatricyclo[7.3.0.03,7]dodeca-1 (9),3,6-triene-6-carbonitrile + TX; 14-methyloctadec-1-ene + TX; [(9Z,1 1 E)-tetradeca-9, 11-dienyl] acetate + TX; [(Z)-dodec-9-enyl] acetate + TX; abamectin + TX; acephate + TX; acequinocyl + TX; acetamiprid + TX; acethion + TX; acetoprole + TX; acibenzolar + TX; acibenzolar-S-methyl + TX; acrinathrin + TX; Adoxophyes orana GV + TX; Agrobacterium radiobacter + TX; alanycarb + TX; albendazole + TX; aldicarb + TX; allethrin + TX; allosamidin + TX; allyl alcohol + TX; allyxycarb + TX; alpha-ecdysone + TX; alpha-multistriatin + TX; Amblyseius spp. + TX; ametoctradin + TX; amidithion + TX; amidoflumet + TX; amidothioate + TX; aminocarb + TX; amisulbrom + TX; amiton + TX; amiton hydrogen oxalate + TX; amitraz + TX; anabasine + TX; Anagrapha falcifera NPV + TX; Anagrus atomus + TX; ancymidol + TX; anilazine + TX; anisiflupurin + TX; anthraquinone + TX; antu + TX; Aphelinus abdominalis + TX; Aphidius colemani + TX; Aphidoletes aphidimyza + TX; athidathion + TX; aureofungin + TX; Autographa californica NPV + TX; avermectin B1 a + TX; azaconazole + TX; azadirachtin A + TX; azafenidin + TX; azamethiphos + TX; azinphos-ethyl + TX; azinphos-methyl + TX; azithiram + TX; azoxystrobin + TX; Bacillus sphaericus (Neide) + TX; Bacillus thuringiensis + TX; Bacillus thuringiensis delta endotoxin + TX; Bacillus thuringiensis ssp. aizawai + TX; baculovirus + TX; barthrin + TX; Beauveria brongniartii + TX; benalaxyl + TX; benalaxyl-M + TX; benazepril + TX; benclothiaz + TX; benfuracarb + TX; benomyl + TX; bensultap + TX; benthiavalicarb + TX; benzalkonium chloride + TX; benzamorf + TX; benzothiostrobin + TX; benzovindiflupyr + TX; beta-cyfluthrin + TX; beta- cypermethrin + TX; bethoxazin + TX; bifenazate + TX; bifenthrin + TX; binapacryl + TX; bioallethrin + TX; bioethanomethrin + TX; biopermethrin + TX; bioresmethrin + TX; bisthiosemi + TX; bistrifluron + TX; bitertanol + TX; bixafen + TX; blasticidin-S + TX; borax + TX; bordeaux mixture + TX; boscalid + TX; brodifacoum + TX; brofenvalerate + TX; brofluthrinate + TX; bromadiolone + TX; bromfenvinfos + TX; bromophos + TX; bromophos-ethyl + TX; bromuconazole + TX; bufencarb + TX; bupirimate + TX; buprofezin + TX; buserelin + TX; busulfan + TX; but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX; butacarb + TX; butathiofos + TX; butocarboxim + TX; butonate + TX; butopyronoxyl + TX; butoxy(polypropylene glycol) + TX; butoxycarboxim + TX; butylamine + TX; cadusafos + TX; calciferol + TX; calcium phosphate + TX; calcium polysulfide + TX; cambendazole + TX; captafol + TX; captan + TX; carbanolate + TX; carbaryl + TX; carbendazim + TX; carbendazim hydrochloride + TX; carbofuran + TX; carbosulfan + TX; carboxin + TX; carprofen + TX; carpropamid + TX; cartap + TX; cartap hydrochloride + TX; cefalexin + TX; cefovecin + TX; cefquinome + TX; ceftiour + TX; cestex + TX; cevadine + TX; chinomethionat + TX; chitosan + TX; chlobenthiazone + TX; chloralose + TX; chlorantraniliprole + TX; chlorbenside + TX; chlordimeform + TX; chlorethephon + TX; chlorethoxyfos + TX; chlorfenapyr + TX; chlorfenazole + TX; chlorfentazine + TX; chlorfenvinphos + TX; chlorfluazuron + TX; chlormephos + TX; chlormequat + TX; chlorodimeform hydrochloride + TX; chloroinconazide + TX; chloromebuform + TX; chloromethiuron + TX; chloroneb + TX; chlorothalonil + TX; chlorphoxim + TX; chlorprazophos + TX; chlorpyrifos + TX; chlorpyrifos-methyl + TX; chlortetracycline + TX; chlorthiophos + TX; chlozolinate + TX; cholecalciferol + TX; chromafenozide + TX; Chrysoperla carnea + TX; cinerin + TX; cinerin I + TX; cinerin II + TX; cis-jasmone + TX; cis- resmethrin + TX; cismethrin + TX; clenbuterol + TX; climbazole + TX; cloethocarb + TX; clofencet + TX; clorsulon + TX; clothianidin + TX; clozylacon (acetamide) + TX; codlelure + TX; copper acetate + TX; copper hydroxide + TX; copper naphthenate + TX; copper octanoate + TX; copper oleate + TX; copper oxide + TX; copper oxychloride + TX; copper silicate + TX; copper sulfate + TX; copper(ll) carbonate + TX; coumachlor + TX; coumafene + TX; coumafuryl + TX; Coumatetralyl + TX; coumethoxystrobin (jiaxiangjunzhi) + TX; coumithoate + TX; coumoxystrobin + TX; cryolite + TX; Cryptolaemus montrouzieri + TX; cuelure + TX; cufraneb + TX; cuprous(l) oxide + TX; cyanofenphos + TX; cyanthoate + TX; cyazofamid + TX; cybutryne + TX; cyclafuramid + TX; cyclethrin + TX; cyclobutrifluram + TX; Cydia pomonella GV + TX; cyenopyrafen + TX; cyflufenamid + TX; cyflumetofen + TX; cyfluthrin + TX; cyhalothrin + TX; cymiazole + TX; cymoxanil + TX; cypermethrin (alphametrin) + TX; cyphenothrin + TX; cyproconazole + TX; cyprodinil + TX; cyprodinil + TX; cyromazine + TX; cytokinins + TX; D-tetramethrin + TX; Dacnusa sibirica + TX; DAEP + TX; dazomet + TX; DCPM + TX; debacarb + TX; decarbofuran + TX; deltamethrin + TX; demephion-O + TX; demephion-S + TX; demeton-O + TX; demeton-S + TX; demeton-S-methyl + TX; demeton-S-methylsulphon + TX; diafenthiuron + TX; dialifos + TX; diazinon + TX; dibutyl adipate + TX; dibutyl phthalate + TX; dibutyl succinate + TX; dicapthon + TX; dichlobentiazox + TX; dichlofluanid + TX; dichlone + TX; dichlorprop + TX; dichlorvos + TX; dichlozoline + TX; diclocymet + TX; diclomezine + TX; dicloran + TX; dicofol + TX; dicresyl + TX; dicrotophos + TX; dicyclanil + TX; dicyclopentadiene + TX; diethofencarb + TX; diethyltoluamide + TX; difenacoum + TX; difenoconazole + TX; difenzoquat + TX; difethialone + TX; diflovidazin + TX; diflubenzuron + TX; diflumetorim + TX; Diglyphus isaea + TX; dimatif + TX; dimefluthrin + TX; dimetan + TX; dimethachlon + TX; dimethipin + TX; dimethirimol + TX; dimethoate + TX; dimethomorph + TX; dimethrin + TX; dimethyl disulfide + TX; dimethyl phthalate + TX; dimetilan + TX; dimoxystrobin + TX; dinactin + TX; diniconazole + TX; diniconazole-M + TX; dinobuton + TX; dinocap + TX; dinocton + TX; dinoseb + TX; dinotefuran + TX; diofenolan + TX; dioxabenzofos + TX; diphenylamine + TX; dipyrithione + TX; disparlure + TX; disulfiram + TX; disulfoton + TX; ditalimfos + TX; dithianon + TX; dithicrofos + TX; dithiocarbamate + TX; dodec- 8-en-1-yl acetate + TX; dodemorph + TX; dodicin + TX; dodine + TX; dofenapyn + TX; dominicalure + TX; doramectin + TX; drazoxolon + TX; DSP + TX; ecdysterone + TX; edifenphos + TX; emamectin benzoate + TX; EMPC + TX; empenthrin + TX; Encarsia formosa + TX; endosulfan + TX; endothal + TX; endothion + TX; enestroburin (enoxastrobin) + TX; enrofloxacin + TX; entomopathogenic bacteria + TX; entomopathogenic fungi + TX; entomopathogenic virus + TX; EPBP + TX; epoxiconazole + TX; eprinomectin + TX; Eretmocerus eremicus + TX; esfenvalerate + TX; etaconazole + TX; ethaboxam + TX; ethiofencarb + TX; ethion + TX; ethiprole + TX; ethirimol + TX; ethoate-methyl + TX; ethoprophos + TX; ethoxyquin + TX; ethyl 4-methyloctanoate + TX; ethyl formate + TX; ethyl hexanediol + TX; etofenprox + TX; etoxazole + TX; etridiazole + TX; etrimfos + TX; eugenol + TX; eurax + TX; EXD + TX; exo-brevicomin + TX; famoxadone + TX; famphur + TX; farnesol with nerolidol + TX; febantel + TX; fenamidone + TX; fenaminstrobin + TX; fenamiphos + TX; fenarimol + TX; fenazaquin + TX; fenbendazole + TX; fenbuconazole + TX; fenbutatin oxide + TX; feneptamidoquin + TX; fenethacarb + TX; fenfluthrin + TX; fenfuram + TX; fenhexamid + TX; fenitrothion + TX; fenobucarb + TX; fenopyramid + TX; fenothiocarb + TX; fenoxacrim + TX; fenoxanil + TX; fenoxycarb + TX; fenpiclonil + TX; fenpicoxamid + TX; fenpirithrin + TX; fenpropathrin + TX; fenpropidin + TX; fenpropimorph + TX; fenpyrazamine + TX; fenpyroximate + TX; fensulfothion + TX; fenthion + TX; tenth ion-ethyl + TX; fentin + TX; fentin acetate + TX; fentin chloride + TX; fentin hydroxide + TX; fenvalerate + TX; ferbam + TX; ferimzone + TX; ferric phosphate + TX; fipronil + TX; flocoumafen + TX; flonicamid + TX; florfenicol + TX; florylpicoxamid + TX; fluacrypyrim + TX; fluazinam + TX; fluazuron + TX; flubendazole + TX; flubendiamide + TX; flubeneteram + TX; flubenzimin + TX; flucycloxuron + TX; flucycloxuron + TX; flucythrinate + TX; fludioxonil + TX; fluenetil + TX; flufenerim + TX; flufenoxuron + TX; flufenoxystrobin + TX; flufenprox + TX; fluindapyr + TX; flumetralin + TX; flumetylsulforim + TX; flumorph + TX; fluopicolide + TX; fluopimomide + TX; fluopyram + TX; fluoroimide + TX; fluoxapiprolin + TX; fluoxastrobin + TX; fluoxytioconazole + TX; flupyrazofos + TX; fluquinconazole + TX; flusilazole + TX; flusulfamide + TX; flutianil + TX; flutolanil + TX; flutriafol + TX; fluxapyroxad + TX; folpet + TX; fonofos + TX; forchlorfenuron + TX; formaldehyde + TX; formetanate + TX; formetanate hydrochloride + TX; formothion + TX; formparanate + TX; fosetyl + TX; fosetyl-aluminium + TX; fosmethilan + TX; fosthiazate + TX; fosthietan + TX; frontalin + TX; fuberidazole + TX; furalaxyl + TX; furametpyr + TX; furathiocarb + TX; furethrin + TX; furfural + TX; gibberellic acid + TX; glyodin + TX; glyphosate + TX; grandlure I + TX; grandlure II + TX; grandlure III + TX; grandlure IV + TX; guazatine triacetate + TX; halfenprox + TX; halofenozide + TX; hemel + TX; heptenophos + TX; Heterorhabditis bacteriophora and H. megidis + TX; hexaconazole + TX; hexadecyl cyclopropanecarboxylate + TX; hexaflumuron + TX; hexalure + TX; hexamide + TX; hexythiazox + TX; Hippodamia convergens + TX; huanjunzuo (rac-(1 S,2S)-1-(4- chlorophenyl)-2-(1 ,2,4-triazol-1-yl)cycloheptanol) + TX; hydramethylnon + TX; hydrated lime (calcium hydroxide) + TX; hymexazol + TX; hyquincarb + TX; icaridin + TX; imanin (hypericin) + TX; imazalil + TX; imazalil sulfate + TX; imibenconazole + TX; imidacloprid + TX; iminoctadine + TX; indoxacarb + TX; inpyrfluxam + TX; iodocarb + TX; ipconazole + TX; ipfentrifluconazole + TX; ipflufenoquin + TX; iprobenfos (IBP) + TX; iprodione + TX; iprovalicarb + TX; ipsdienol + TX; ipsenol + TX; IPSP + TX; isamidofos + TX; isazofos + TX; isocarbophos + TX; isofetamid + TX; isoflucypram + TX; isolan + TX; isoprocarb + TX; isoprothiolane + TX; isopyrazam + TX; isothioate + TX; isotianil + TX; isoxathion + TX; ivermectin + TX; japonilure + TX; jasmolin I + TX; jasmolin II + TX; juvenile hormone I + TX; juvenile hormone II + TX; juvenile hormone III + TX; kadethrin + TX; kanamycin + TX; kasugamycin + TX; kasugamycin hydrochloride hydrate + TX; kinetin + TX; kinoprene + TX; kresoxim-methyl + TX; kurstaki + TX; lambda-cyhalothrin + TX; Leptomastix dactylopii + TX; leptophos + TX; levamisole + TX; lineatin + TX; lirimfos + TX; looplure + TX; lufenuron + TX; Ivbenmixianan + TX; lythidathion + TX; m-cumenyl methylcarbamate + TX; Macrolophus caliginosus + TX; magnesium phosphide + TX; malathion + TX; maleic hydrazide + TX; malonoben + TX; Mamestra brassicae NPV + TX; mancopper + TX; mancozeb + TX; mandestrobin + TX; mandipropamid + TX; maneb + TX; mazidox + TX; mebendazole + TX; mecarbam + TX; mecarphon + TX; medlure + TX; mefentrifluconazole + TX; megatomoic acid + TX; meloxicam + TX; menazon + TX; mepanipyrim + TX; meperfluthrin + TX; mephosfolan + TX; mepiquat + TX; mepronil + TX; meptyldinocap + TX; mesulfenfos + TX; metaflumizone + TX; metalaxyl + TX; metalaxyl-M + TX; metaldehyde + TX; metam + TX; metam-potassium + TX; metam-sodium + TX; Metaphycus helvolus + TX; Metarhizium anisopliae var. acridum + TX; Metarhizium anisopliae var. anisopliae + TX; metarylpicoxamid + TX; metconazole + TX; methacrifos + TX; methamidophos + TX; methasulfocarb + TX; methidathion + TX; methiocarb + TX; methiotepa + TX; methocrotophos + TX; methomyl + TX; methoprene + TX; methoquin-butyl + TX; methothrin + TX; methoxyfenozide + TX; methyl apholate + TX; methyl eugenol + TX; methyl iodide + TX; methyl neodecanamide + TX; metiram + TX; metofluthrin + TX; metolcarb + TX; metominostrobin + TX; metoxadiazone + TX; metrafenone + TX; metyltetraprole + TX; mevinphos + TX; mexacarbate + TX; MGK 264 + TX; milbemycin + TX; milbemycin oxime + TX; monocrotophos + TX; morantel tartrate + TX; morzid + TX; moxidectin + TX; muscalure + TX; myclobutanil + TX; myclozolin + TX; Myrothecium verrucaria composition + TX; N-[2- [2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX; N- cyclopropyl-3-(difluoromethyl)-5-fluoro-N-[(2-isopropylphenyl)methyl]-1-methyl-pyrazole-4- carboxamide + TX; nabam + TX; naled + TX; NC-170 + TX; nemadectin + TX; Neodiprion sertifer NPV and N. lecontei NPV + TX; niclosamide-olamine + TX; nicotine + TX; nicotine sulfate + TX; nikkomycins + TX; nitenpyram + TX; nithiazine + TX; nitrapyrin + TX; nitrilacarb + TX; nitrothal-isopropyl + TX; norbormide + TX; nornicotine + TX; novaluron + TX; noviflumuron + TX; nuarimol + TX; O,O,O',O'- tetrapropyl dithiopyrophosphate + TX; octadeca-2,13-dien-1-yl acetate + TX; octadeca-2,13-dien-1-yl acetate + TX; octhilinone + TX; ofurace + TX; oleic acid + TX; omethoate + TX; orfralure + TX; Orius spp. + TX; orysastrobin + TX; osthol + TX; ostramone + TX; oxadixyl + TX; oxamate + TX; oxamyl + TX; oxantel pamoate + TX; oxasulfuron + TX; oxathiapiprolin + TX; oxfendazole + TX; oxibendazole + TX; oxine copper + TX; oxolinic acid + TX; oxpoconazole + TX; oxycarboxin + TX; oxydemeton-methyl + TX; oxydeprofos + TX; oxydisulfoton + TX; oxytetracycline + TX; oxytetracycline dihydrate + TX; paclobutrazol + TX; Paecilomyces fumosoroseus + TX; paraoxon + TX; parathion + TX; parathion- methyl + TX; parbendazole + TX; pefurazoate + TX; penconazole + TX; pencycuron + TX; penethamate + TX; penflufen + TX; penthiopyrad + TX; permethrin + TX; petroleum oils + TX; PH 60-38 + TX; phenamacril + TX; phenthoate + TX; phorate + TX; phosacetim + TX; phosalone + TX; phosfolan + TX; phosglycin + TX; phosmet + TX; phosnichlor + TX; phosphamidon + TX; phosphocarb + TX; phosphonic acid + TX; phosphorus + TX; phoxim + TX; phoxim-methyl + TX; phthalide + TX; Phytoseiulus persimilis + TX; picarbutrazox+ TX; picoxystrobin + TX; pimobendan + TX; pindone + TX; piperalin + TX; piperonyl butoxide + TX; piprotal + TX; pirimetaphos + TX; pirimicarb + TX; pirimiphos-methyl + TX; polycarbamate + TX; polynactin + TX; polyoxin B + TX; polyoxin d + TX; potassium ethylxanthate + TX; potassium hydroxyquinoline sulfate + TX; praziquantel + TX; precocene I + TX; precocene II + TX; precocene III + TX; primidophos + TX; probenazole + TX; prochloraz + TX; procymidone + TX; profenofos + TX; profluthrin + TX; prohexadione + TX; prohexadione-calcium + TX; promacyl + TX; promecarb + TX; propamidine + TX; propamocarb + TX; propaphos + TX; propargite + TX; propetamphos + TX; propiconazole + TX; propineb + TX; propionic acid + TX; propoxur + TX; propyl isomer + TX; proquinazid + TX; prothidathion + TX; proth ioconazole + TX; prothiofos + TX; prothoate + TX; protrifenbute + TX; pydiflumetofen + TX; pymetrozine + TX; pyraclofos + TX; pyraclostrobin + TX; pyrafluprole + TX; pyrametostrobin + TX; pyrantel pamoate + TX; pyraoxystrobin + TX; pyrapropoyne + TX; pyraziflumid + TX; pyrazophos + TX; pyrazoxone + TX; pyresmethrin + TX; pyrethrin I + TX; pyrethrin II + TX; pyrethrins (natural products) + TX; pyrethroids (natural products) + TX; pyribencarb + TX; pyridaben + TX; pyridachlometyl + TX; pyridalyl + TX; pyridaphenthion + TX; pyridin-4-amine + TX; pyrifenox + TX; pyrifluquinazon + TX; pyrimethanil + TX; pyrimidifen + TX; pyrimorph + TX; pyriofenone + TX; pyriprole + TX; pyriproxyfen + TX; pyrisoxazole + TX; pyroquilon + TX; quassia + TX; quinalphos + TX; quinalphos-methyl + TX; quinoclamine + TX; quinofumelin + TX; quinonamid + TX; quinothion + TX; quinoxyfen + TX; quintozene + TX; R-1492 + TX; R-metalaxyl + TX; Reynoutria sachalinensis extract + TX; ribavirin + TX; rotenone + TX; ryanodine (ryania) + TX; sabadilla + TX; schradan + TX; scilliroside + TX; seboctylamine + TX; sedaxane + TX; selamectin + TX; sesamex + TX; sesamolin + TX; siglure + TX; silafluofen + TX; silthiofam + TX; simeconazole + TX; sodium tetrathiocarbonate + TX; sophamide + TX; sordidin + TX; spinetoram + TX; spinosad + TX; spirodiclofen + TX; spiromesifen + TX; spirotetramat + TX; spiroxamine + TX; Steinernema bibionis + TX; Steinernema carpocapsae + TX; Steinernema feltiae + TX; Steinernema glaseri + TX; Steinernema riobrave + TX; Steinernema riobravis + TX; Steinernema scapterisci + TX; Steinernema spp. + TX; streptomycin + TX; streptomycin sesquisulfate + TX; sulcatol + TX; sulcofuron + TX; sulfiram + TX; sulfur + TX; sulprofos + TX; tar oils + TX; tau-fluvalinate + TX; TCMTB + TX; TDE + TX; tebuconazole + TX; tebufenozide + TX; tebufenpyrad + TX; tebufloquin + TX; tebupirimfos + TX; tecnazene + TX; teflubenzuron + TX; tefluthrin + TX; temephos + TX; terallethrin + TX; terbam + TX; terbufos + TX; tetrachlorvinphos + TX; tetraconazole + TX; tetradec-11-en-1-yl acetate + TX; tetradifon + TX; tetramethrin + TX; tetramethylfluthrin + TX; tetranactin + TX; thiabendazole + TX; thiacloprid + TX; thiadiazole copper + TX; thiamethoxam + TX; thiapronil + TX; thicrofos + TX; thicyofen + TX; thidiazuron + TX; thifluzamide + TX; thiocarboxime + TX; thiocyclam + TX; thiocyclam hydrogen oxalate + TX; thiodicarb + TX; thiofanox + TX; thiometon + TX; thiophanate + TX; thiophanate-methyl + TX; thioquinox + TX; thiosultap + TX; thiosultap-disodium + TX; thiram + TX; thuringiensin + TX; tiadinil + TX; tiamulin + TX; tioxymid + TX; tolclofos-methyl + TX; tolfenpyrad + TX; tolprocarb + TX; tolylfluanid + TX; tralomethrin + TX; transpermethrin + TX; tretamine + TX; triadimefon + TX; triadimenol + TX; triarathene + TX; triazamate + TX; triazophos + TX; triazoxide + TX; tribufos + TX; trichlorfon + TX; trichlormetaphos-3 + TX; trichloronat + TX; Trichogramma spp. + TX; triclabendazole + TX; triclopyricarb + TX; tricyclazole + TX; tridemorph + TX; trifenmorph + TX; trifloxystrobin + TX; triflumizole + TX; triflumuron + TX; triforine + TX; trimedlure + TX; trimedlure A + TX; trimedlure B1 + TX; trimedlure B2 + TX; trimedlure C + TX; trimethacarb + TX; trinactin + TX; trinexapac + TX; trinexapac-ethyl + TX; triprene + TX; triticonazole + TX; trunc-call + TX; tulathromycin + TX; Typhlodromus occidentalis + TX; uniconazole + TX; uredepa + TX; validamycin + TX; valifenalate + TX; vamidothion + TX; vaniliprole + TX; veratridine + TX; veratrine + TX; verbutin + TX; Verticillium lecanii + TX; vinclozolin + TX; XMC + TX; xylenols + TX; zeatin + TX; zeta-cypermethrin + TX; zhongshengmycin + TX; zinc naphthenate + TX; zinc thiazole + TX; zineb + TX; ziram + TX; zolaprofos + TX; zoxamide + TX; 2-(difluoromethyl)-N-[(3S)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3- carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX; methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy-1 -methyl-2-(1 , 2 ,4-triazol- 1 - ylmethyl)cyclopentanecarboxylate (this compound may be prepared from the methods described in WO 2019/093522) + TX; methyl (2R)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1- yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522) + TX; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; aminopyrifen (this compound may be prepared from the methods described in WO 2014/006945) + TX; dipymetitrone (this compound may be prepared from the methods described in WO 2011/138281) + TX; 1-[6- (difluoromethyl)-5-methyl-3-pyridyl]-4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915) + TX; 1-[4-(difluoromethoxy)-2-methyl- phenyl]-2-(1 ,2,4-triazol-1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from the methods described in WO 2021/249800) + TX; 1-[2-chloro-4-(difluoromethoxy)phenyl]-2-(1 ,2,4- triazol-1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from the methods described in WO 2021/249800) + TX; 1-(5,6-dimethyl-3-pyridyl)-4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915) + TX; N-methyl-4- [5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzenecarbothioamide (this compound may be prepared from the methods described in WO 2015/185485) + TX; 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2017/178245) + TX; flufenoxadiazam + TX; N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]benzamide (this compound may be prepared from the methods described in WO 2015/185485) + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018/153707) + TX; (Z,2E)-5-[1-(4- chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2013/092224) + TX; methyl (2E)-2-methoxyimino-2-[3- methyl-2-[[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl]acetate (this compound may be prepared from the methods described in WO 2022/033906) + TX; (2E)-2- methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-1-[4-(trifluoromethyl)-2- pyridyl]ethylideneamino]oxymethyl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2022/033906) + TX; (2E)-2-[2-[[(E)-[3-(4-fluorophenyl)-1-methyl-prop-2- ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide (this compound may be prepared from the methods described in WO 2021/249928) + TX; methyl (2E)-2-[2-[[(E)-[3-(4- fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (this compound may be prepared from the methods described in WO 2021/249928) + TX; 3-[2-(1- chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX; 3-[2-(1- chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX; 2-[6-(4-bromophenoxy)-2- (trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1- (1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)ethyl]pyrimidin-2- amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; 5-[5- (difluoromethyl)-l ,3,4-oxadiazol-2-yl]-N-[1 -(3,5-difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; N-[1-(2- fluorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,3,4-oxadiazol-2-yl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; 5-[5-(difluoromethyl)-1 ,3,4- oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; 2-(difluoromethyl)-5-[2-[1-(2,6- difluorophenyl)cyclopropoxy]pyrimidin-5-yl]-1 ,3,4-oxadiazole (this compound may be prepared from the methods described in WO 2021/255093) + TX; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2- fluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX; 5-[(4-bromo-2-methyl-phenyl)methyl]-3-[3-(3-chloro-2-fluoro- phenoxy)-6-methyl-pyridazin-4-yl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2021/255070) + TX; 3-[3-(3-cyclopropyl-2-fluoro-phenoxy)-6-methyl- pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2021/255070) + TX; N-(2,2,2-trifluoroethyl)-2-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]oxazole-4-carboxamide (this compound may be prepared from the methods described in WO 2022/133114) + TX; ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenoxy]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2022/133114) + TX; ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1- enoxy]phenyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021/183707) + TX; ethyl 1-[[4-[[2-(trifluoromethyl)-1 ,3- dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021/183707) + TX; methyl N-[[5-[4-(2,4- dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX; methyl N-[[5-[1-(2,6-difluoro-4-isopropyl- phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX; methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro- phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX; methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2- hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522) + TX; 4,4,5-trifluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline + TX; 5-fluoro-3, 3,4,4- tetramethyl-1-(3-quinolyl)isoquinoline + TX; 2-methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-thienyl]methyl]acetamide (this compound may be prepared from the methods described in WO 2020/256113) + TX; N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]-2-methyl-propanamide (this compound may be prepared from the methods described in WO 2020/256113) + TX; N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]butanamide (this compound may be prepared from the methods described in WO 2020/256113) + TX; 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX; 2- (difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX; 2-(difluoromethyl)-N-(1 ,1 ,3- trimethylindan-4-yl)pyridine-3-carboxamide + TX; (5R)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl- pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070) + TX; (5S)-3-[3- (3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro- 4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070) + TX; 3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2- chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070) + TX; methyl (Z)-3-methoxy-2-(2- methyl-5-phenyl-phenoxy)prop-2-enoate (this compound may be prepared from methods as described in JP2023078251) +TX; 2-[(2,6-difluoro-4-pyridyl)-(2-methylpropanoyl)amino]-N-(2,2- dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof +TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); 2-[(2,6-difluoro-4-pyridyl)-
(tetrahydropyran-4-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof +TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); 2- [cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof +TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109509A1); 2-[cyano-(2,6-difluoro-4- pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof +TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109509A1); 2-[(2,6-difluoro-4-pyridyl)-(2- methoxyacetyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof +TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); 2-[acetyl-(2,6- difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide + TX; or the (R) or (S) enantiomer or mixtures thereof +TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511 A1 , WO2021244952A1); N-methoxy-N-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (this compound may be prepared from the methods described in WO 2017/055473) +TX; N-[(1 R)-1-benzyl-1 ,3-dimethylbutyl]- 8-fluoroquinoline-3-carboxamide (this compound may be prepared from the methods described in WO2017/153380) +TX; N-[(1 S)-1-benzyl-1 ,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide (this compound may be prepared from the methods described in WO2017/153380) +TX; 2-[(2,6-difluoro-4- pyridyl)-(oxetane-3-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (/?) or (S) enantiomer or mixtures thereof +TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); 2- [acetyl-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX; or the (/?) or (S) enantiomer or mixtures thereof +TX (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); N,2- dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX; or the (/?) or (S) enantiomer or mixtures thereof +TX (this compound may be prepared from the methods described in WO 2017/055473).
Further disclosed are two-way mixture compositions, wherein the term “TX1” represent the compound methyl (E)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate: a composition selected from the group consisting of (4E,10Z)-tetradeca-4, 10-dienyl acetate + TX1 ; (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX1 ; (E)-6-methylhept-2-en-4-ol + TX1 ; (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX1 ; (E)-tridec-4-en-1-yl acetate + TX1 ; (S)-bioallethrin + TX1 ; (Z)-dodec-7-en-1-yl acetate + TX1 ; (Z)- hexadec-11-en-1-yl acetate + TX1 ; (Z)-hexadec-l 1-enal + TX1 ; (Z)-hexadec-13-en-11-yn-1-yl acetate + TX1 ; (Z)-icos-13-en-10-one + TX1 ; (Z)-tetradec-7-en-1-al + TX1 ; (Z)-tetradec-9-en-1-ol + TX1 ; (Z)- tetradec-9-en-1-yl acetate + TX1 ; 1 ,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX1 ; 1-(2-chlorophenyl)-
3.3-dimethyl-2-(1 ,2,4-triazol-1-ylmethyl)butan-2-ol + TX1 ; 1-(5-bromo-2-pyridyl)-2-(2,4-difluorophenyl)- 1 ,1-difluoro-3-(1 ,2,4-triazol-1-yl)propan-2-ol + TX1 ; 1 -hydroxy-1 H-pyridine-2-thione + TX1 ; 1- methylcyclopropene + TX1 ; 1 -naphthaleneacetamide + TX1 ; 1 -naphthylacetic acid + TX1 ; 2,2- dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX1 ; 2,4-D + TX1 ; 2,4-DB + TX1 ; 2,6-dichloro-N- (4-trifluormethylbenzyl)benzamide + TX1 ; 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX1 ; 2-(2- butoxyethoxy)ethyl piperonylate + TX1 ; 2-(4,5-dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate + TX1 ; 2-(difluoromethyl)-N-((3R)-1 ,1 ,3-trimethylindan-4-yl) pyridine-3-carboxamide + TX1 ; 2- (octylthio)-ethanol + TX1 ; 2-bromo-2-bromomethyl-pentanedinitrile + TX1 ; 2-chlorovinyl diethyl phosphate + TX1 ; 2-imidazolidone + TX1 ; 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX1 ; 2-thiocyanatoethyl laurate + TX1 ; 3-(4-chlorophenyl)-5-methylrhodanine + TX1 ; 3-(difluoromethyl)-1- methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX1 ; 3-(difluoromethyl)-N-(7-fluoro-
1 .1 .3.3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide + TX1 ; 3-(difluoromethyl)-N-(7-fluoro- 1 ,1 ,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide + TX1 ; 3-chloro-6-methyl-5-phenyl-4- (2,4,6-trifluorophenyl)pyridazine + TX1 ; 3-methyl-1-phenylpyrazol-5-yl dimethyl-carbamate + TX1 ; 3- phenylphenol + TX1 ; 4,5-dichlorodithiol-3-one + TX1 ; 4-(2,6-difluorophenyl)-6-methyl-5-phenyl- pyridazine-3-carbonitrile + TX1 ; 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl- pyrazol-3-amine + TX1 ; 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX1 ; 4-[[6-[2-(2,4- difluorophenyl)-1 , 1 -difluoro-2-hydroxy-3-(1 , 2 ,4-tri azo I- 1 -yl)propyl]-3-pyridyl]oxy]benzonitrile + TX1 ; 4- chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX1 ; 4-CPA + TX1 ;
4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX1 ; 4-methylnonan-5-ol with 4-methylnonan-
5-one + TX1 ; 4-phenylphenol + TX1 ; 5-(1 ,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX1 ; 5-amino- 1 ,3,4-thiadiazole-2-thiol + TX1 ; 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine + TX1 ; 5-hydroxy-6- methyl-4-(((E)-pyridin-3-ylmethylene)amino)-4,5-dihydro-1 ,2,4-triazin-3(2H)-one + TX1 ; 5-methyl-6- thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid + TX1 ; 8-hydroxyquinoline sulfate + TX1 ; 11-ethyl-10,12-dioxo- 2,5,8-trithia-4,11-diazatricyclo[7.3.0.03,7]dodeca-1(9),3,6-triene-6-carbonitrile + TX1; 14- methyloctadec-1-ene + TX1 ; [(9Z,11 E)-tetradeca-9,11 -dienyl] acetate + TX1 ; [(Z)-dodec-9-enyl] acetate + TX1; abamectin + TX1; acephate + TX1; acequinocyl + TX1; acetamiprid + TX1; acethion + TX1; acetoprole + TX1; acibenzolar + TX1; acibenzolar-S-methyl + TX1; acrinathrin + TX1; Adoxophyes orana GV + TX1; Agrobacterium radiobacter + TX1; alanycarb + TX1; albendazole + TX1; aldicarb + TX1; allethrin + TX1; allosamidin + TX1; allyl alcohol + TX1; allyxycarb + TX1; alpha-ecdysone + TX1; alpha-multistriatin + TX1; Amblyseius spp. + TX1; ametoctradin + TX1; amidithion + TX1; amidoflumet + TX1; amidothioate + TX1; aminocarb + TX1; amisulbrom + TX1; amiton + TX1; amiton hydrogen oxalate + TX1 ; amitraz + TX1 ; anabasine + TX1 ; Anagrapha falcifera NPV + TX1 ; Anagrus atomus + TX1; ancymidol + TX1; anilazine + TX1; anisiflupurin + TX1; anthraquinone + TX1; antu + TX1; Aphelinus abdominalis + TX1; Aphidius colemani + TX1; Aphidoletes aphidimyza + TX1; athidathion + TX1; aureofungin + TX1; Autographa californica NPV + TX1; avermectin B1a + TX1; azaconazole + TX1 ; azadirachtin A + TX1 ; azafenidin + TX1 ; azamethiphos + TX1 ; azinphos-ethyl + TX1 ; azinphos- methyl + TX1; azithiram + TX1; azoxystrobin + TX1; Bacillus sphaericus (Neide) + TX1; Bacillus thuringiensis + TX1; Bacillus thuringiensis delta endotoxin + TX1; Bacillus thuringiensis ssp. aizawai + TX1; baculovirus + TX1; barthrin + TX1; Beauveria brongniartii + TX1; benalaxyl + TX1; benalaxyl-M + TX1; benazepril + TX1; benclothiaz + TX1; benfuracarb + TX1; benomyl + TX1; bensultap + TX1; benthiavalicarb + TX1; benzalkonium chloride + TX1; benzamorf + TX1; benzothiostrobin + TX1; benzovindiflupyr + TX1 ; beta-cyfluthrin + TX1 ; beta-cypermethrin + TX1 ; bethoxazin + TX1 ; bifenazate + TX1 ; bifenthrin + TX1 ; binapacryl + TX1 ; bioallethrin + TX1 ; bioethanomethrin + TX1 ; biopermethrin + TX1; bioresmethrin + TX1; bisthiosemi + TX1; bistrifluron + TX1; bitertanol + TX1; bixafen + TX1; blasticidin-S + TX1; borax + TX1; bordeaux mixture + TX1; boscalid + TX1; brodifacoum + TX1; brofenvalerate + TX1 ; brofluthrinate + TX1 ; bromadiolone + TX1 ; bromfenvinfos + TX1 ; bromophos + TX1 ; bromophos-ethyl + TX1 ; bromuconazole + TX1 ; bufencarb + TX1 ; bupirimate + TX1 ; buprofezin + TX1; buserelin + TX1; busulfan + TX1; but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX1; butacarb + TX1; butathiofos + TX1; butocarboxim + TX1; butonate + TX1; butopyronoxyl + TX1; butoxy(polypropylene glycol) + TX1; butoxycarboxim + TX1 ; butylamine + TX1 ; cadusafos + TX1 ; calciferol + TX1 ; calcium phosphate + TX1 ; calcium polysulfide + TX1; cambendazole + TX1; captafol + TX1; captan + TX1; carbanolate + TX1; carbaryl + TX1 ; carbendazim + TX1 ; carbendazim hydrochloride + TX1 ; carbofuran + TX1 ; carbosulfan + TX1 ; carboxin + TX1 ; carprofen + TX1 ; carpropamid + TX1 ; cartap + TX1 ; cartap hydrochloride + TX1 ; cefalexin + TX1; cefovecin + TX1; cefquinome + TX1; ceftiour + TX1; cestex + TX1; cevadine + TX1; chinomethionat + TX1; chitosan + TX1; chlobenthiazone + TX1; chloralose + TX1; chlorantraniliprole + TX1; chlorbenside + TX1; chlordimeform + TX1; chlorethephon + TX1; chlorethoxyfos + TX1; chlorfenapyr + TX1; chlorfenazole + TX1; chlorfentazine + TX1; chlorfenvinphos + TX1; chlorfluazuron + TX1 ; chlormephos + TX1 ; chlormequat + TX1 ; chlorodimeform hydrochloride + TX1 ; chloroinconazide + TX1; chloromebuform + TX1; chloromethiuron + TX1; chloroneb + TX1; chlorothalonil + TX1; chlorphoxim + TX1; chlorprazophos + TX1; chlorpyrifos + TX1; chlorpyrifos-methyl + TX1; chlortetracycline + TX1 ; chlorthiophos + TX1 ; chlozolinate + TX1 ; cholecalciferol + TX1 ; chromafenozide + TX1; Chrysoperla carnea + TX1; cinerin + TX1; cinerin I + TX1; cinerin II + TX1; cis-jasmone + TX1; cis-resmethrin + TX1; cismethrin + TX1; clenbuterol + TX1; climbazole + TX1; cloethocarb + TX1; clofencet + TX1; clorsulon + TX1; clothianidin + TX1; clozylacon (acetamide) + TX1; codlelure + TX1; copper acetate + TX1; copper hydroxide + TX1; copper naphthenate + TX1; copper octanoate + TX1; copper oleate + TX1; copper oxide + TX1; copper oxychloride + TX1; copper silicate + TX1; copper sulfate + TX1; copper(ll) carbonate + TX1; coumachlor + TX1; coumafene + TX1; coumafuryl + TX1; Coumatetralyl + TX1; coumethoxystrobin (jiaxiangjunzhi) + TX1; coumithoate + TX1; coumoxystrobin + TX1 ; cryolite + TX1 ; Cryptolaemus montrouzieri + TX1 ; cuelure + TX1 ; cufraneb + TX1 ; cuprous(l) oxide + TX1; cyanofenphos + TX1; cyanthoate + TX1; cyazofamid + TX1; cybutryne + TX1; cyclafuramid + TX1; cyclethrin + TX1; cyclobutrifluram + TX1; Cydia pomonella GV + TX1; cyenopyrafen + TX1; cyflufenamid + TX1; cyflumetofen + TX1; cyfluthrin + TX1; cyhalothrin + TX1; cymiazole + TX1; cymoxanil + TX1; cypermethrin (alphametrin) + TX1; cyphenothrin + TX1; cyproconazole + TX1; cyprodinil + TX1 ; cyprodinil + TX1 ; cyromazine + TX1 ; cytokinins + TX1 ; D-tetramethrin + TX1 ; Dacnusa sibirica + TX1; DAEP + TX1; dazomet + TX1; DCPM + TX1; debacarb + TX1; decarbofuran + TX1; deltamethrin + TX1; demephion-O + TX1; demephion-S + TX1; demeton-O + TX1; demeton-S + TX1; demeton-S-methyl + TX1; demeton-S-methylsulphon + TX1; diafenthiuron + TX1; dialifos + TX1; diazinon + TX1 ; dibutyl adipate + TX1 ; dibutyl phthalate + TX1 ; dibutyl succinate + TX1 ; dicapthon + TX1 ; dichlobentiazox + TX1 ; dichlofluanid + TX1 ; dichlone + TX1 ; dichlorprop + TX1 ; dichlorvos + TX1 ; dichlozoline + TX1 ; diclocymet + TX1 ; diclomezine + TX1 ; dicloran + TX1 ; dicofol + TX1 ; dicresyl + TX1 ; dicrotophos + TX1 ; dicyclanil + TX1 ; dicyclopentadiene + TX1 ; diethofencarb + TX1 ; diethyltoluamide + TX1 ; difenacoum + TX1 ; difenoconazole + TX1 ; difenzoquat + TX1 ; difethialone + TX1 ; diflovidazin + TX1 ; diflubenzuron + TX1 ; diflumetorim + TX1 ; Diglyphus isaea + TX1 ; dimatif + TX1 ; dimefluthrin + TX1; dimetan + TX1; dimethachlon + TX1; dimethipin + TX1; dimethirimol + TX1; dimethoate + TX1; dimethomorph + TX1; dimethrin + TX1; dimethyl disulfide + TX1; dimethyl phthalate + TX1; dimetilan + TX1 ; dimoxystrobin + TX1 ; dinactin + TX1 ; diniconazole + TX1 ; diniconazole-M + TX1 ; dinobuton + TX1 ; dinocap + TX1 ; dinocton + TX1 ; dinoseb + TX1 ; dinotefuran + TX1 ; diofenolan + TX1 ; dioxabenzofos + TX1; diphenylamine + TX1; dipyrithione + TX1; disparlure + TX1; disulfiram + TX1; disulfoton + TX1; ditalimfos + TX1 ; dithianon + TX1 ; dithicrofos + TX1 ; dithiocarbamate + TX1 ; dodec-8-en-1-yl acetate + TX1; dodemorph + TX1; dodicin + TX1; dodine + TX1; dofenapyn + TX1; dominicalure + TX1; doramectin + TX1; drazoxolon + TX1; DSP + TX1; ecdysterone + TX1; edifenphos + TX1; emamectin benzoate + TX1 ; EMPC + TX1 ; empenthrin + TX1 ; Encarsia formosa + TX1 ; endosulfan + TX1 ; endothal + TX1; endothion + TX1; enestroburin (enoxastrobin) + TX1; enrofloxacin + TX1; entomopathogenic bacteria + TX1; entomopathogenic fungi + TX1; entomopathogenic virus + TX1; EPBP + TX1; epoxiconazole + TX1; eprinomectin + TX1; Eretmocerus eremicus + TX1; esfenvalerate + TX1; etaconazole + TX1 ; ethaboxam + TX1 ; ethiofencarb + TX1 ; ethion + TX1 ; ethiprole + TX1 ; ethirimol + TX1; ethoate-methyl + TX1; ethoprophos + TX1; ethoxyquin + TX1; ethyl 4-methyloctanoate + TX1; ethyl formate + TX1; ethyl hexanediol + TX1; etofenprox + TX1; etoxazole + TX1; etridiazole + TX1; etrimfos + TX1 ; eugenol + TX1 ; eurax + TX1 ; EXD + TX1 ; exo-brevicomin + TX1 ; famoxadone + TX1 ; famphur + TX1 ; farnesol with nerolidol + TX1 ; febantel + TX1 ; fenamidone + TX1 ; fenaminstrobin + TX1 ; fenamiphos + TX1 ; fenarimol + TX1 ; fenazaquin + TX1 ; fenbendazole + TX1 ; fenbuconazole + TX1 ; fenbutatin oxide + TX1 ; feneptamidoquin + TX1 ; fenethacarb + TX1 ; fenfluthrin + TX1 ; fenfuram + TX1 ; fenhexamid + TX1; fenitrothion + TX1; fenobucarb + TX1; fenopyramid + TX1; fenothiocarb + TX1; fenoxacrim + TX1; fenoxanil + TX1; fenoxycarb + TX1; fenpiclonil + TX1; fenpicoxamid + TX1; fenpirithrin + TX1 ; fenpropathrin + TX1 ; fenpropidin + TX1 ; fenpropimorph + TX1 ; fenpyrazamine + TX1 ; fenpyroximate + TX1; fensulfothion + TX1; fenthion + TX1; tenth ion-ethyl + TX1; fentin + TX1; fentin acetate + TX1; fentin chloride + TX1; fentin hydroxide + TX1; fenvalerate + TX1; ferbam + TX1; ferimzone + TX1 ; ferric phosphate + TX1 ; fipronil + TX1 ; flocoumafen + TX1 ; flonicamid + TX1 ; florfenicol + TX1; florylpicoxamid + TX1; fluacrypyrim + TX1; fluazinam + TX1; fluazuron + TX1; flubendazole + TX1 ; flubendiamide + TX1 ; flubeneteram + TX1 ; flubenzimin + TX1 ; flucycloxuron + TX1 ; flucycloxuron + TX1 ; flucythrinate + TX1 ; fludioxonil + TX1 ; fluenetil + TX1 ; flufenerim + TX1 ; flufenoxuron + TX1 ; flufenoxystrobin + TX1; flufenprox + TX1; fluindapyr + TX1; flumetralin + TX1; flumetylsulforim + TX1; flumorph + TX1; fluopicolide + TX1; fluopimomide + TX1; fluopyram + TX1; fluoroimide + TX1; fluoxapiprolin + TX1 ; fluoxastrobin + TX1 ; fluoxytioconazole + TX1 ; flupyrazofos + TX1 ; fluquinconazole + TX1; flusilazole + TX1; flusulfamide + TX1; flutianil + TX1; flutolanil + TX1; flutriafol + TX1; fluxapyroxad + TX1; folpet + TX1; fonofos + TX1; forchlorfenuron + TX1; formaldehyde + TX1; formetanate + TX1 ; formetanate hydrochloride + TX1 ; formothion + TX1 ; formparanate + TX1 ; fosetyl + TX1 ; fosetyl-aluminium + TX1 ; fosmethilan + TX1 ; fosthiazate + TX1 ; fosthietan + TX1 ; frontalin + TX1 ; fuberidazole + TX1; furalaxyl + TX1; furametpyr + TX1; furathiocarb + TX1; furethrin + TX1; furfural + TX1; gibberellic acid + TX1; glyodin + TX1; glyphosate + TX1; grandlure I + TX1; grandlure II + TX1; grandlure III + TX1 ; grandlure IV + TX1 ; guazatine triacetate + TX1 ; halfenprox + TX1 ; halofenozide + TX1; hemel + TX1; heptenophos + TX1; Heterorhabditis bacteriophora and H. megidis + TX1; hexaconazole + TX1 ; hexadecyl cyclopropanecarboxylate + TX1 ; hexaflumuron + TX1 ; hexalure + TX1 ; hexamide + TX1; hexythiazox + TX1; Hippodamia convergens + TX1; huanjunzuo (rac-(1S,2S)-1-(4- chlorophenyl)-2-(1 , 2 ,4-tri azo I- 1 -yl)cycloheptanol) + TX1 ; hydramethylnon + TX1 ; hydrated lime (calcium hydroxide) + TX1 ; hymexazol + TX1 ; hyquincarb + TX1 ; icaridin + TX1 ; imanin (hypericin) + TX1 ; imazalil + TX1; imazalil sulfate + TX1; imibenconazole + TX1; imidacloprid + TX1; iminoctadine + TX1; indoxacarb + TX1 ; inpyrfluxam + TX1 ; iodocarb + TX1 ; ipconazole + TX1 ; ipfentrifluconazole + TX1 ; ipflufenoquin + TX1; iprobenfos (IBP) + TX1; iprodione + TX1; iprovalicarb + TX1; ipsdienol + TX1; ipsenol + TX1 ; IPSP + TX1 ; isamidofos + TX1 ; isazofos + TX1 ; isocarbophos + TX1 ; isofetamid + TX1 ; isoflucypram + TX1 ; isolan + TX1 ; isoprocarb + TX1 ; isoprothiolane + TX1 ; isopyrazam + TX1 ; isothioate + TX1 ; isotianil + TX1 ; isoxathion + TX1 ; ivermectin + TX1 ; japonilure + TX1 ; jasmolin I + TX1 ; jasmolin II + TX1 ; juvenile hormone I + TX1 ; juvenile hormone II + TX1 ; juvenile hormone III + TX1 ; kadethrin + TX1 ; kanamycin + TX1 ; kasugamycin + TX1 ; kasugamycin hydrochloride hydrate + TX1 ; kinetin + TX1 ; kinoprene + TX1; kresoxim-methyl + TX1; kurstaki + TX1; lambda-cyhalothrin + TX1; Leptomastix dactylopii + TX1 ; leptophos + TX1 ; levamisole + TX1 ; lineatin + TX1 ; lirimfos + TX1 ; looplure + TX1 ; lufenuron + TX1; Ivbenmixianan + TX1; lythidathion + TX1; m-cumenyl methylcarbamate + TX1; Macrolophus caliginosus + TX1; magnesium phosphide + TX1; malathion + TX1; maleic hydrazide + TX1; malonoben + TX1; Mamestra brassicae NPV + TX1; mancopper + TX1; mancozeb + TX1; mandestrobin + TX1; mandipropamid + TX1; maneb + TX1; mazidox + TX1; mebendazole + TX1; mecarbam + TX1; mecarphon + TX1; medlure + TX1; mefentrifluconazole + TX1; megatomoic acid + TX1 ; meloxicam + TX1 ; menazon + TX1 ; mepanipyrim + TX1 ; meperfluthrin + TX1 ; mephosfolan + TX1 ; mepiquat + TX1; mepronil + TX1; meptyldinocap + TX1; mesulfenfos + TX1; metaflumizone + TX1; metalaxyl + TX1; metalaxyl-M + TX1; metaldehyde + TX1; metam + TX1; metam-potassium + TX1; metam-sodium + TX1; Metaphycus helvolus + TX1; Metarhizium anisopliae var. acridum + TX1; Metarhizium anisopliae var. anisopliae + TX1 ; metarylpicoxamid + TX1 ; metconazole + TX1 ; methacrifos + TX1; methamidophos + TX1; methasulfocarb + TX1; methidathion + TX1; methiocarb + TX1; methiotepa + TX1; methocrotophos + TX1; methomyl + TX1; methoprene + TX1; methoquin-butyl + TX1 ; methothrin + TX1 ; methoxyfenozide + TX1 ; methyl apholate + TX1 ; methyl eugenol + TX1 ; methyl iodide + TX1; methyl neodecanamide + TX1; metiram + TX1; metofluthrin + TX1; metolcarb + TX1; metominostrobin + TX1; metoxadiazone + TX1; metrafenone + TX1; metyltetraprole + TX1; mevinphos + TX1; mexacarbate + TX1; MGK 264 + TX1; milbemycin + TX1; milbemycin oxime + TX1; monocrotophos + TX1; morantel tartrate + TX1; morzid + TX1; moxidectin + TX1; muscalure + TX1; myclobutanil + TX1; myclozolin + TX1; Myrothecium verrucaria composition + TX1; N-[2-[2,4-dichloro- phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX1; N-cyclopropyl-3- (difluoromethyl)-5-fluoro-N-[(2-isopropylphenyl)methyl]-1 -methyl-pyrazole-4-carboxamide + TX1 ; nabam + TX1 ; naled + TX1 ; NC-170 + TX1 ; nemadectin + TX1 ; Neodiprion sertifer NPV and N. lecontei NPV + TX1; niclosamide-olamine + TX1; nicotine + TX1; nicotine sulfate + TX1; nikkomycins + TX1; nitenpyram + TX1; nithiazine + TX1; nitrapyrin + TX1; nitrilacarb + TX1; nitrothal-isopropyl + TX1; norbormide + TX1 ; nornicotine + TX1 ; novaluron + TX1 ; noviflumuron + TX1 ; nuarimol + TX1 ; O,O,O',O'- tetrapropyl dithiopyrophosphate + TX1; octadeca-2,13-dien-1-yl acetate + TX1; octadeca-2,13-dien-1- yl acetate + TX1 ; octhilinone + TX1 ; ofurace + TX1 ; oleic acid + TX1 ; omethoate + TX1 ; orfralure + TX1 ; Orius spp. + TX1 ; orysastrobin + TX1 ; osthol + TX1 ; ostramone + TX1 ; oxadixyl + TX1 ; oxamate + TX1 ; oxamyl + TX1; oxantel pamoate + TX1; oxasulfuron + TX1; oxathiapiprolin + TX1; oxfendazole + TX1; oxibendazole + TX1 ; oxine copper + TX1 ; oxolinic acid + TX1 ; oxpoconazole + TX1 ; oxycarboxin + TX1 ; oxydemeton-methyl + TX1; oxydeprofos + TX1; oxydisulfoton + TX1; oxytetracycline + TX1; oxytetracycline dihydrate + TX1; paclobutrazol + TX1; Paecilomyces fumosoroseus + TX1; paraoxon + TX1 ; parathion + TX1 ; parathion-methyl + TX1 ; parbendazole + TX1 ; pefurazoate + TX1 ; penconazole + TX1; pencycuron + TX1; penethamate + TX1; penflufen + TX1; penthiopyrad + TX1; permethrin + TX1; petroleum oils + TX1; PH 60-38 + TX1; phenamacril + TX1; phenthoate + TX1; phorate + TX1; phosacetim + TX1 ; phosalone + TX1 ; phosfolan + TX1 ; phosglycin + TX1 ; phosmet + TX1 ; phosnichlor + TX1 ; phosphamidon + TX1 ; phosphocarb + TX1 ; phosphonic acid + TX1 ; phosphorus + TX1 ; phoxim + TX1; phoxim-methyl + TX1; phthalide + TX1; Phytoseiulus persimilis + TX1; picarbutrazox + TX1; picoxystrobin + TX1; pimobendan + TX1; pindone + TX1; piperalin + TX1; piperonyl butoxide + TX1; piprotal + TX1; pirimetaphos + TX1; pirimicarb + TX1; pirimiphos-methyl + TX1; polycarbamate + TX1; polynactin + TX1; polyoxin B + TX1; polyoxin d + TX1; potassium ethylxanthate + TX1; potassium hydroxyquinoline sulfate + TX1 ; praziquantel + TX1 ; precocene I + TX1 ; precocene II + TX1 ; precocene III + TX1 ; primidophos + TX1 ; probenazole + TX1 ; prochloraz + TX1 ; procymidone + TX1 ; profenofos + TX1 ; profluthrin + TX1 ; prohexadione + TX1 ; prohexadione-calcium + TX1 ; promacyl + TX1 ; promecarb + TX1 ; propamidine + TX1 ; propamocarb + TX1 ; propaphos + TX1 ; propargite + TX1 ; propetamphos + TX1 ; propiconazole + TX1 ; propineb + TX1 ; propionic acid + TX1 ; propoxur + TX1 ; propyl isomer + TX1 ; proquinazid + TX1; prothidathion + TX1; prothioconazole + TX1; prothiofos + TX1; prothoate + TX1; protrifenbute + TX1 ; pydiflumetofen + TX1 ; pymetrozine + TX1 ; pyraclofos + TX1 ; pyraclostrobin + TX1 ; pyrafluprole + TX1; pyrametostrobin + TX1; pyrantel pamoate + TX1; pyraoxystrobin + TX1; pyrapropoyne + TX1; pyraziflumid + TX1; pyrazophos + TX1; pyrazoxone + TX1; pyresmethrin + TX1; pyrethrin I + TX1; pyrethrin II + TX1; pyrethrins (natural products) + TX1; pyrethroids (natural products) + TX1 ; pyribencarb + TX1 ; pyridaben + TX1 ; pyridachlometyl + TX1 ; pyridalyl + TX1 ; pyridaphenthion + TX1 ; pyridin-4-amine + TX1 ; pyrifenox + TX1 ; pyrifluquinazon + TX1 ; pyrimethanil + TX1 ; pyrimidifen + TX1; pyrimorph + TX1; pyriofenone + TX1; pyriprole + TX1; pyriproxyfen + TX1; pyrisoxazole + TX1; pyroquilon + TX1; quassia + TX1; quinalphos + TX1; quinalphos-methyl + TX1; quinoclamine + TX1; quinofumelin + TX1; quinonamid + TX1; quinothion + TX1; quinoxyfen + TX1; quintozene + TX1; R- 1492 + TX1; R-metalaxyl + TX1; Reynoutria sachalinensis extract + TX1; ribavirin + TX1; rotenone + TX1; ryanodine (ryania) + TX1; sabadilla + TX1; schradan + TX1; scilliroside + TX1; seboctylamine + TX1 ; sedaxane + TX1 ; selamectin + TX1 ; sesamex + TX1 ; sesamolin + TX1 ; siglure + TX1 ; silafluofen + TX1; silthiofam + TX1; simeconazole + TX1; sodium tetrathiocarbonate + TX1; sophamide + TX1; sordidin + TX1; spinetoram + TX1; spinosad + TX1; spirodiclofen + TX1; spiromesifen + TX1; spirotetramat + TX1 ; spiroxamine + TX1 ; Steinernema bibionis + TX1 ; Steinernema carpocapsae + TX1 ; Steinernema feltiae + TX1; Steinernema glaseri + TX1; Steinernema riobrave + TX1; Steinernema riobravis + TX1; Steinernema scapterisci + TX1; Steinernema spp. + TX1; streptomycin + TX1; streptomycin sesquisulfate + TX1; sulcatol + TX1; sulcofuron + TX1; sulfiram + TX1; sulfur + TX1; sulprofos + TX1 ; tar oils + TX1 ; tau-fluvalinate + TX1 ; TCMTB + TX1 ; TDE + TX1 ; tebuconazole + TX1 ; tebufenozide + TX1; tebufenpyrad + TX1; tebufloquin + TX1; tebupirimfos + TX1; tecnazene + TX1; teflubenzuron + TX1; tefluthrin + TX1; temephos + TX1; terallethrin + TX1; terbam + TX1; terbufos + TX1 ; tetrachlorvinphos + TX1 ; tetraconazole + TX1 ; tetradec-11 -en-1 -yl acetate + TX1 ; tetradifon + TX1 ; tetramethrin + TX1 ; tetramethylfluthrin + TX1 ; tetranactin + TX1 ; thiabendazole + TX1 ; thiacloprid + TX1 ; thiadiazole copper + TX1; thiamethoxam + TX1; thiapronil + TX1; thicrofos + TX1; thicyofen + TX1; thidiazuron + TX1; thifluzamide + TX1; thiocarboxime + TX1; thiocyclam + TX1; thiocyclam hydrogen oxalate + TX1; thiodicarb + TX1; thiofanox + TX1; thiometon + TX1; thiophanate + TX1; thiophanate- methyl + TX1; thioquinox + TX1; thiosultap + TX1; thiosultap-disodium + TX1; thiram + TX1; thuringiensin + TX1 ; tiadinil + TX1 ; tiamulin + TX1 ; tioxymid + TX1 ; tolclofos-methyl + TX1 ; tolfenpyrad + TX1; tolprocarb + TX1; tolylfluanid + TX1; tralomethrin + TX1; transpermethrin + TX1; tretamine + TX1 ; triadimefon + TX1 ; triadimenol + TX1 ; triarathene + TX1 ; triazamate + TX1 ; triazophos + TX1 ; triazoxide + TX1; tribufos + TX1; trichlorfon + TX1; trichlormetaphos-3 + TX1; trichloronat + TX1; Trichogramma spp. + TX1; triclabendazole + TX1; triclopyricarb + TX1; tricyclazole + TX1; tridemorph + TX1; trifenmorph + TX1; trifloxystrobin + TX1; triflumizole + TX1; triflumuron + TX1; triforine + TX1; trimedlure + TX1; trimedlure A + TX1; trimedlure B1 + TX1; trimedlure B2 + TX1; trimedlure C + TX1; trimethacarb + TX1; trinactin + TX1; trinexapac + TX1; trinexapac-ethyl + TX1; triprene + TX1; triticonazole + TX1; trunc-call + TX1; tulathromycin + TX1; Typhlodromus occidentalis + TX1; uniconazole + TX1; uredepa + TX1; validamycin + TX1; valifenalate + TX1; vamidothion + TX1; vaniliprole + TX1; veratridine + TX1; veratrine + TX1; verbutin + TX1; Verticillium lecanii + TX1; vinclozolin + TX1; XMC + TX1; xylenols + TX1; zeatin + TX1; zeta-cypermethrin + TX1; zhongshengmycin + TX1; zinc naphthenate + TX1; zinc thiazole + TX1; zineb + TX1; ziram + TX1; zolaprofos + TX1; zoxamide + TX1; 2-(difluoromethyl)-N-[(3S)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine- 3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX1 ; methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1 ,2,4-triazol-1 - ylmethyl)cyclopentanecarboxylate (this compound may be prepared from the methods described in WO 2019/093522) + TX1 ; methyl (2R)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1- yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522) + TX1 ; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1 -(2,6-difluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX1 ; aminopyrifen (this compound may be prepared from the methods described in WO 2014/006945) + TX1 ; dipymetitrone (this compound may be prepared from the methods described in WO 2011/138281) + TX1 ; 1-[6-(difluoromethyl)-5-methyl-3-pyridyl]-4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915) + TX1 ; 1-[4-(difluoromethoxy)-2- methyl-phenyl]-2-(1 ,2,4-triazol-1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from the methods described in WO 2021/249800) + TX1 ; 1-[2-chloro-4- (difluoromethoxy)phenyl]-2-(1 ,2,4-triazol-1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from the methods described in WO 2021/249800) + TX1 ; 1-(5,6-dimethyl-3-pyridyl)- 4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915) + TX1 ; N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzenecarbothioamide (this compound may be prepared from the methods described in WO 2015/185485) + TX1 ; 2,2-difluoro- N-methyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2017/178245) + TX1 ; flufenoxadiazam + TX1 ; N-methyl- 4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide (this compound may be prepared from the methods described in WO 2015/185485) + TX1 ; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2- methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018/153707) + TX1 ; (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino- N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2013/092224) + TX1 ; methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-1-[4-(trifluoromethyl)-2- pyridyl]ethylideneamino]oxymethyl]phenyl]acetate (this compound may be prepared from the methods described in WO 2022/033906) + TX1 ; (2E)-2-methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-1-[4- (trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2022/033906) + TX1 ; (2E)-2-[2-[[(E)-[3-(4-fluorophenyl)-1- methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide (this compound may be prepared from the methods described in WO 2021/249928) + TX1 ; methyl (2E)-2-[2- [[(E)-[3-(4-fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2- methoxyimino-acetate (this compound may be prepared from the methods described in WO 2021/249928) + TX1 ; 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy- propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX1 ; 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4- carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX1 ; 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX1 ; 2-[6-(4-chlorophenoxy)-2- (trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX1 ; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2- fluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX1 ; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(3,5- difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX1 ; N-[1-(2-fluorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,3,4-oxadiazol-2- yl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX1 ; 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX1 ; 2- (difluoromethyl)-5-[2-[1-(2,6-difluorophenyl)cyclopropoxy]pyrimidin-5-yl]-1 ,3,4-oxadiazole (this compound may be prepared from the methods described in WO 2021/255093) + TX1 ; 5-[5- (difluoromethyl)-l ,3,4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX1 ; 5-[(4-bromo-2- methyl-phenyl)methyl]-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5,6-dihydro-4H-1 ,2,4- oxadiazine (this compound may be prepared from the methods described in WO 2021/255070) + TX1 ; 3-[3-(3-cyclopropyl-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6- dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2021/255070) + TX1 ; N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]oxazole-4-carboxamide (this compound may be prepared from the methods described in WO 2022/133114) + TX1 ; ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenoxy]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2022/133114) + TX1 ; ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1- enoxy]phenyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021/183707) + TX1 ; ethyl 1-[[4-[[2-(trifluoromethyl)-1 ,3- dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021/183707) + TX1 ; methyl N-[[5-[4-(2,4- dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX1 ; methyl N-[[5-[1-(2,6-difluoro-4-isopropyl- phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX1 ; methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro- phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX1 ; methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2- hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522) + TX1 ; 4,4,5-trifluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline + TX1 ; 5-fluoro-
3.3.4.4-tetramethyl-1-(3-quinolyl)isoquinoline + TX1 ; 2-methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-
1 .2.4-oxadiazol-3-yl]-2-thienyl]methyl]acetamide (this compound may be prepared from the methods described in WO 2020/256113) + TX1 ; N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]-2-methyl-propanamide (this compound may be prepared from the methods described in WO 2020/256113) + TX1 ; N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]butanamide (this compound may be prepared from the methods described in WO 2020/256113) + TX1 ; 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3- carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX1 ; 2-(difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX1 ; 2-(difluoromethyl)-N-(1 ,1 ,3- trimethylindan-4-yl)pyridine-3-carboxamide + TX1 ; (5R)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl- pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070) + TX1 ; (5S)-3- [3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6- dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070) + TX1 ; 3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5- [(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070) + TX1 ; methyl (Z)-3-methoxy-2- (2-methyl-5-phenyl-phenoxy)prop-2-enoate (this compound may be prepared from methods as described in JP2023078251) +TX1 ; 2-[(2,6-difluoro-4-pyridyl)-(2-methylpropanoyl)amino]-N-(2,2- dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX1 ; or the (/?) or (S) enantiomer or mixtures thereof +TX1 (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); 2-[(2,6-difluoro-4-pyridyl)-
(tetrahydropyran-4-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX1 ; or the (/?) or (S) enantiomer or mixtures thereof +TX1 (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 ,
WO2021244952A1); 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4- carboxamide + TX1 ; or the (/?) or (S) enantiomer or mixtures thereof +TX1 (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109509A1); 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX1 ; or the (/?) or (S) enantiomer or mixtures thereof +TX1 (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109509A1); 2-[(2,6-difluoro-4- pyridyl)-(2-methoxyacetyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX1 ; or the (/?) or (S) enantiomer or mixtures thereof +TX1 (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 ,
WO2021244952A1); 2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4- carboxamide + TX1 ; or the (/?) or (S) enantiomer or mixtures thereof +TX1 (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); N-methoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]cyclopropanecarboxamide (this compound may be prepared from the methods described in WO 2017/055473) +TX1 ; methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop- 2-enoate (this compound may be prepared from the methods described in W02020/193387) +TX1 ; methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (this compound may be prepared from the methods described in W02020/193387) +TX1 ; N-[(1 R)-1-benzyl-1 ,3-dimethylbutyl]- 8-fluoroquinoline-3-carboxamide (this compound may be prepared from the methods described in WO2017/153380) +TX1 ; N-[(1S)-1-benzyl-1 ,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide (this compound may be prepared from the methods described in WO2017/153380) +TX1 ; 2-[(2,6-difluoro-4- pyridyl)-(oxetane-3-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX1 ; or the (/?) or (S) enantiomer or mixtures thereof +TX1 (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 ,
WO2021244952A1); 2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl- thiazole-4-carboxamide + TX1 ; or the (/?) or (S) enantiomer or mixtures thereof +TX1 (this compound may be prepared from the methods described in WO2017207362A1 , WO2019105933A1 , W02020109511A1 , WO2021244952A1); N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]methyl]propanamide + TX1 ; or the (/?) or (S) enantiomer or mixtures thereof +TX1 (this compound may be prepared from the methods described in WO 2017/055473).
In another aspect to the present invention, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, mancozeb, chlorothalonil, fluazinam, fluxapyroxad, isopyrazam, sedaxane, boscalid, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, inpyrfluxam, mefentrifluconazole, florylpicoxamid, metarylpicoxamid and metyltetraprole, or a salt, enantiomer, tautomer or N-oxide thereof.
Preferably, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of acibenzolar-S-methyl, cyproconazole, difenoconazole, hexaconazole, prothioconazole, tebuconazole, fenpropidin, azoxystrobin, trifloxystrobin, mancozeb, chlorothalonil, fluazinam, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, metarylpicoxamid and metyltetraprole, or a salt, enantiomer, tautomer or N-oxide thereof.
More preferably, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of cyproconazole, difenoconazole, prothioconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil and flufenoxadiazam, or a salt, enantiomer, tautomer or N-oxide thereof.
Even more preferably, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of difenoconazole, prothioconazole, tebuconazole, fenpropidin and chlorothalonil, or a salt, enantiomer, tautomer or N-oxide thereof.
In another aspect to the present invention, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, mancozeb, chlorothalonil, fluazinam, fluxapyroxad, isopyrazam, sedaxane, boscalid, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, inpyrfluxam, mefentrifluconazole, florylpicoxamid, metarylpicoxamid, metyltetraprole, (5R)-3-[3-(3-chloro-2-fluoro- phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4- oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), (5S)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl- phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), 3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl- pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), methyl (Z)-3- methoxy-2-(2-methyl-5-phenyl-phenoxy)prop-2-enoate (this compound may be prepared from methods as described in JP2023078251), ethyl 1-[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2- yl]methoxy]phenyl]methyl]-1 H-pyrazole-4-carboxylate (this compound may be prepared from methods as described in WO 2021/183707), ethyl 1 -[[4-[[(1 Z)-2-ethoxy-3, 3, 3-trifluoro-1 -propen-1 - yl]oxy]phenyl]methyl]-1 H-pyrazole-4-carboxylate (this compound may be prepared from methods as described in WO 2021/183707), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6- difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from methods as described in from WO 2021/255093), 2-(difluoromethyl)-5-[2-[1-(2,6-difluorophenyl)cyclopropoxy]pyrimidin-5-yl]-
1 .3.4-oxadiazole (this compound may be prepared from methods as described in WO 2021/255093), 5- [5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), 5-[5-(difluoromethyl)-
1 .3.4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), N-[1-(2-fluorophenyl)cyclopropyl]-5-[5- (trifluoromethyl)-l ,3,4-oxadiazol-2-yl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2- fluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(3,5-difluorophenyl)ethyl]pyrimidin- 2-amine (this compound may be prepared from methods as described in WO 2021/255093), N-methoxy- N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (this compound may be prepared from the methods described in WO 2017/055473), N,2-dimethoxy-N-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO 2017/055473), methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy-1 -methyl-2-(1 , 2 ,4-triazol- 1 - ylmethyl)cyclopentanecarboxylate (this compound may be prepared from the methods described in WO 2019/093522), methyl (2R)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1 - yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522); methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 , 2 ,4-triazol- 1 -yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522), 1-[4-(difluoromethoxy)- 2-methyl-phenyl]-2-(1 ,2,4-triazol-1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from methods as described in WO 2021/249800), methyl (2E)-2-methoxyimino-2-[3-methyl-2- [[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl]acetate (this compound may be prepared from methods as described in WO 2022/033906), (2E)-2-methoxyimino-N-methyl-2-[3-methyl- 2-[[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl]acetamide (this compound may be prepared from methods as described in WO 2022/033906), methyl (2E)-2-[2-[[(E)-[3-(4- fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (this compound may be prepared from methods as described in WO 2021/249928), (2E)-2-[2-[[(E)-[3- (4-fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N- methyl-acetamide (this compound may be prepared from methods as described in WO 2021/249928), methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from methods as described in WO 2020/097012), methyl N-[[5-[1-(4- cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from methods as described in WO 2020/097012), N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-thienyl]methyl]butanamide (this compound may be prepared from methods as described in WO 2020/256113), 2-methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]acetamide (this compound may be prepared from methods as described in WO 2020/256113) and N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]-2-methyl- propanamide (this compound may be prepared from methods as described in from WO 2020/256113) or a salt, enantiomer, tautomer or N-oxide thereof.
In another aspect to the present invention, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, mancozeb, chlorothalonil, fluazinam, fluxapyroxad, isopyrazam, sedaxane, boscalid, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, inpyrfluxam, mefentrifluconazole, florylpicoxamid, metarylpicoxamid and metyltetraprole, or a salt, enantiomer, tautomer or N-oxide thereof.
Preferably, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of acibenzolar-S-methyl, cyproconazole, difenoconazole, hexaconazole, prothioconazole, tebuconazole, fenpropidin, azoxystrobin, trifloxystrobin, mancozeb, chlorothalonil, fluazinam, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, metarylpicoxamid and metyltetraprole, or a salt, enantiomer, tautomer or N-oxide thereof. More preferably, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of cyproconazole, difenoconazole, prothioconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil and flufenoxadiazam, or a salt, enantiomer, tautomer or N-oxide thereof.
Even more preferably, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of difenoconazole, prothioconazole, tebuconazole, fenpropidin and chlorothalonil, or a salt, enantiomer, tautomer or N-oxide thereof.
In another aspect to the present invention, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, mancozeb, chlorothalonil, fluazinam, fluxapyroxad, isopyrazam, sedaxane, boscalid, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, inpyrfluxam, mefentrifluconazole, florylpicoxamid, metarylpicoxamid, metyltetraprole, (5R)-3-[3-(3-chloro-2-fluoro- phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4- oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), (5S)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl- phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), 3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl- pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), methyl (Z)-3- methoxy-2-(2-methyl-5-phenyl-phenoxy)prop-2-enoate (this compound may be prepared from methods as described in JP2023078251), ethyl 1-[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2- yl]methoxy]phenyl]methyl]-1 H-pyrazole-4-carboxylate (this compound may be prepared from methods as described in WO 2021/183707), ethyl 1 -[[4-[[(1 Z)-2-ethoxy-3, 3, 3-trifluoro-1 -propen-1 - yl]oxy]phenyl]methyl]-1 H-pyrazole-4-carboxylate (this compound may be prepared from methods as described in WO 2021/183707), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6- difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from methods as described in from WO 2021/255093), 2-(difluoromethyl)-5-[2-[1-(2,6-difluorophenyl)cyclopropoxy]pyrimidin-5-yl]- 1 ,3,4-oxadiazole (this compound may be prepared from methods as described in WO 2021/255093), 5- [5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), 5-[5-(difluoromethyl)- 1 ,3,4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), N-[1-(2-fluorophenyl)cyclopropyl]-5-[5- (trifluoromethyl)-l ,3,4-oxadiazol-2-yl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2- fluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(3,5-difluorophenyl)ethyl]pyrimidin- 2-amine (this compound may be prepared from methods as described in WO 2021/255093), N-methoxy- N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (this compound may be prepared from the methods described in WO 2017/055473), N,2-dimethoxy-N-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO 2017/055473), methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy-1 -methyl-2-(1 , 2 ,4-triazol- 1 - ylmethyl)cyclopentanecarboxylate (this compound may be prepared from the methods described in WO 2019/093522), methyl (2R)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1 - yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522); methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 , 2 ,4-triazol- 1 -yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522), 1-[4-(difluoromethoxy)- 2-methyl-phenyl]-2-(1 ,2,4-triazol-1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from methods as described in WO 2021/249800), methyl (2E)-2-methoxyimino-2-[3-methyl-2- [[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl]acetate (this compound may be prepared from methods as described in WO 2022/033906), (2E)-2-methoxyimino-N-methyl-2-[3-methyl- 2-[[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl]acetamide (this compound may be prepared from methods as described in WO 2022/033906), methyl (2E)-2-[2-[[(E)-[3-(4- fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (this compound may be prepared from methods as described in WO 2021/249928), (2E)-2-[2-[[(E)-[3- (4-fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N- methyl-acetamide (this compound may be prepared from methods as described in WO 2021/249928), methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from methods as described in WO 2020/097012), methyl N-[[5-[1-(4- cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from methods as described in WO 2020/097012), N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-thienyl]methyl]butanamide (this compound may be prepared from methods as described in WO 2020/2561 13), 2-methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]acetamide (this compound may be prepared from methods as described in WO 2020/256113) and N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]-2-methyl- propanamide (this compound may be prepared from methods as described in from WO 2020/256113) or a salt, enantiomer, tautomer or N-oxide thereof. In another aspect to the present invention, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, mancozeb, chlorothalonil, fluazinam, fluxapyroxad, isopyrazam, sedaxane, boscalid, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, inpyrfluxam, mefentrifluconazole, florylpicoxamid, metarylpicoxamid and metyltetraprole, or a salt, enantiomer, tautomer or N-oxide thereof.
Preferably, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (C) as active ingredients, wherein component (B) is a compound selected from the group consisting of acibenzolar-S-methyl, cyproconazole, difenoconazole, hexaconazole, prothioconazole, tebuconazole, fenpropidin, azoxystrobin, trifloxystrobin, mancozeb, chlorothalonil, fluazinam, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, metarylpicoxamid and metyltetraprole, or a salt, enantiomer, tautomer or N-oxide thereof.
More preferably, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (C) as active ingredients, wherein component (B) is a compound selected from the group consisting of cyproconazole, difenoconazole, prothioconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil and flufenoxadiazam, or a salt, enantiomer, tautomer or N-oxide thereof.
Even more preferably, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, as component (A) and a component (C) as active ingredients, wherein component (B) is a compound selected from the group consisting of difenoconazole, prothioconazole, tebuconazole, fenpropidin and chlorothalonil, or a salt, enantiomer, tautomer or N-oxide thereof.
In another aspect to the present invention, there is provided a fungicidal composition comprising a mixture of a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein, as component (A) and a component (B) as active ingredients, wherein component (B) is a compound selected from the group consisting of bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, prothioconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, mancozeb, chlorothalonil, fluazinam, fluxapyroxad, isopyrazam, sedaxane, boscalid, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, inpyrfluxam, mefentrifluconazole, florylpicoxamid, metarylpicoxamid, metyltetraprole, (5R)-3-[3-(3-chloro-2-fluoro- phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4- oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), (5S)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl- phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), 3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl- pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780, WO 2021/255070), methyl (Z)-3- methoxy-2-(2-methyl-5-phenyl-phenoxy)prop-2-enoate (this compound may be prepared from methods as described in JP2023078251), ethyl 1-[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2- yl]methoxy]phenyl]methyl]-1 H-pyrazole-4-carboxylate (this compound may be prepared from methods as described in WO 2021/183707), ethyl 1 -[[4-[[(1 Z)-2-ethoxy-3, 3, 3-trifluoro-1 -propen-1 - yl]oxy]phenyl]methyl]-1 H-pyrazole-4-carboxylate (this compound may be prepared from methods as described in WO 2021/183707), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6- difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from methods as described in from WO 2021/255093), 2-(difluoromethyl)-5-[2-[1-(2,6-difluorophenyl)cyclopropoxy]pyrimidin-5-yl]-
1 .3.4-oxadiazole (this compound may be prepared from methods as described in WO 2021/255093), 5- [5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6-difluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), 5-[5-(difluoromethyl)-
1 .3.4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), N-[1-(2-fluorophenyl)cyclopropyl]-5-[5- (trifluoromethyl)-l ,3,4-oxadiazol-2-yl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2- fluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from methods as described in WO 2021/255093), 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(3,5-difluorophenyl)ethyl]pyrimidin- 2-amine (this compound may be prepared from methods as described in WO 2021/255093), N-methoxy- N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (this compound may be prepared from the methods described in WO 2017/055473), N,2-dimethoxy-N-[[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO 2017/055473), methyl 3-[(4-chlorophenyl)methyl]-2-hydroxy-1 -methyl-2-(1 , 2 ,4-triazol- 1 - ylmethyl)cyclopentanecarboxylate (this compound may be prepared from the methods described in WO 2019/093522), methyl (2R)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1 - yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522); methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 , 2 ,4-triazol- 1 -yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522), 1-[4-(difluoromethoxy)- 2-methyl-phenyl]-2-(1 ,2,4-triazol-1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from methods as described in WO 2021/249800), methyl (2E)-2-methoxyimino-2-[3-methyl-2- [[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl]acetate (this compound may be prepared from methods as described in WO 2022/033906), (2E)-2-methoxyimino-N-methyl-2-[3-methyl- 2-[[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl]acetamide (this compound may be prepared from methods as described in WO 2022/033906), methyl (2E)-2-[2-[[(E)-[3-(4- fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (this compound may be prepared from methods as described in WO 2021/249928), (2E)-2-[2-[[(E)-[3- (4-fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N- methyl-acetamide (this compound may be prepared from methods as described in WO 2021/249928), methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from methods as described in WO 2020/097012), methyl N-[[5-[1-(4- cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from methods as described in WO 2020/097012), N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-thienyl]methyl]butanamide (this compound may be prepared from methods as described in WO 2020/256113), 2-methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]acetamide (this compound may be prepared from methods as described in WO 2020/256113) and N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]-2-methyl- propanamide (this compound may be prepared from methods as described in from WO 2020/256113) or a salt, enantiomer, tautomer or N-oxide thereof.
In general, the weight ratio of component (A) to component (B) may be from 1000: 1 to 1 :1000, may be from 100:1 to 1 :100, preferably from 50:1 to 1 :50, more preferably from 20:1 to 1 :40, even more preferably from 15:1 to 1 :30, still more preferably from 12:1 to 1 :25, or from 10:1 to 1 :20, or from 10:1 to 1 :10, or from 5:1 and 1 :15, or from 5:1 to 1 :5, or from 4:1 to 1 :4, or from 3:1 to 1 :10, or from 3:1 to 1 :3, or from 2:1 to 1 :5, or 1 :1.
In one embodiment preferred fungicidal compositions used in the method of the invention comprising a mixture of components (A) and (B) are disclosed in Tables M1 and M2 below.
Table M1 - Specific Fungicidal Compositions
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Table M2 - Specific Fungicidal Compositions
Figure imgf000073_0002
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
The preferred ratio ranges for preferred compositions used in the method of the invention are given in Tables R1 and R2 below. * Where component (B) exists in alternative forms (e.g salt I ester) then it should be understood that these can be substituted. Table R1 : Exemplar ratio ranges for specific compositions used in the method of the invention
Figure imgf000079_0001
Figure imgf000080_0001
Table R2: Exemplar ratio ranges for specific compositions used in the method of the invention
Figure imgf000081_0001
Figure imgf000082_0001
In any of the compositions according to the invention, the composition may comprise an additional active ingredient component (C), which is different to component (B), and is selected from the group consisting of bixafen, fenpyrazamine, copper sulfate, copper hydroxide, triclopyricarb, acibenzolar, acibenzolar-S- methyl, copper oxychloride, copper oxide, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, fenarimol, nuarimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, azoxystrobin, dimoxystrobin, fenaminstrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, mancozeb, chlorothalonil, cyclobutrifluram, famoxadone, fenamidone, fluazinam, fluoxytioconazole, fluxapyroxad, fenhexamid, pyribencarb, triforine, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, mandestrobin, pyraziflumid, inpyrfluxam, mefentrifluconazole, ipfentrifluconazole, penflufen, florylpicoxamid, metarylpicoxamid, isofetamid, ethyl 1-[[4-[[2- (trifluoromethyl)-l ,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate, ethyl 1 -[[4-[(Z)-2- ethoxy-3,3,3-trifluoro-prop-1 -enoxy]phenyl]methyl]pyrazole-3-carboxylate, methyl N-[[4-[1 -(4- cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate, methyl N-[[4-[1-(2,6- difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate, fluopyram, flufenoxadiazam, metyltetraprole, enoxastrobin, coumoxystrobin, N'-[5-bromo-2-methyl-6-[(1 S)-1- methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1 R)-1- methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-
2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2- propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2- propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(2- propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N-isopropyl-N’-[5-methoxy-2-methyl-4- (2, 2, 2-trifl u o ro- 1 -hydroxy-1 -phenyl-ethyl)phenyl]-N-methyl-formamidine, N’-[4-(1 -cyclopropyl-2,2,2- trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine, N-ethyl-N’- [5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N’-[5- methoxy-2-methyl-4-[(2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine, N-[(1 R)-1- benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 S)-1-benzyl-3-chloro-1- methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 R)-1 -benzyl-3,3,3-trifluoro-1 -methyl-propyl]- 8-fluoro-quinoline-3-carboxamide, N-[(1 S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-
3-carboxamide, N-[(1 R)-1-benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide,
N-[(1 S)-1-benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1 R)-1-[(3- fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1 S)-1 -[(3- fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1 R)-1 -benzyl- 1 ,3-dimethyl-butyl]- 8-fluoro-quinoline-3-carboxamide, N-[(1 S)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3- carboxamide, N-((1 R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1 S)-1-benzyl-3- chloro-1 -methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, 1 -(6,7-dimethylpyrazolo[1 ,5-a]pyridin-3- yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,6-trifluoro-
3.3-dimethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline,
4.4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl- pyrazolo[1 ,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 1 -(4,5-dimethylbenzimidazol-1-yl)- 4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl- isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro- 1 -(5-fluoro-4-methyl-benzimidazol-1 -yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1 - isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3- py ridy I]- 1 -(1 , 2 ,4-tri azo I- 1 -yl)propan-2-ol, 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1 -(1 ,2,4- triazol-1-yl)propan-2-ol, 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4- carbonitrile, 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4- carbonitrile, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone, (3- methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone, 2-oxo-N-propyl-2- [4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide, ethyl 1-[[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-
1 .2.4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]benzamide and N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]benzamide.
The component (C) compounds are referred to herein and above by a so-called "ISO common name" or another "common name" being used in individual cases or a trademark name. The component (C) compounds are known and are commercially available and/or can be prepared using procedures known in the art.
In another aspect to the present invention, there is provided a fungicidal composition comprising a mixture of components (A), (B) and (C) as active ingredients, wherein component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, and wherein component (B) is the compound difenoconazole or prothioconazole; and wherein component (C) is a compound selected from the group consisting of cyproconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil, benzovindiflupyr and pydiflumetofen.
In another aspect to the present invention, there is provided a fungicidal composition comprising a mixture of components (A), (B) and (C) as active ingredients, wherein component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, and wherein component (B) is the compound difenoconazole or prothioconazole; and wherein component (C) is a compound selected from the group consisting of cyproconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil, benzovindiflupyr and pydiflumetofen.
In another aspect to the present invention, there is provided a fungicidal composition comprising a mixture of components (A), (B) and (C) as active ingredients, wherein component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2- enoate as defined herein, and wherein component (B) is the compound difenoconazole or prothioconazole; and wherein component (C) is a compound selected from the group consisting of cyproconazole, tebuconazole, fenpropidin, mancozeb, chlorothalonil, benzovindiflupyr and pydiflumetofen.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound mancozeb.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound prothioconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound mancozeb.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound difenoconazole. In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound chlorothalonil.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound pydiflumetofen.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound mancozeb; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound chlorothalonil.
In one embodiment of the invention component (A) is a crystalline polymorph (form A) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound cyproconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound mancozeb.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound prothioconazole. In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound mancozeb.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound chlorothalonil.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound pydiflumetofen.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound mancozeb; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound chlorothalonil.
In one embodiment of the invention component (A) is a crystalline polymorph (form B) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound cyproconazole. In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound mancozeb.
In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound tebuconazole; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound prothioconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound benzovindiflupyr; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound mancozeb.
In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound chlorothalonil.
In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound prothioconazole; and component (C) is the compound pydiflumetofen. In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound mancozeb; and component (C) is the compound difenoconazole.
In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component (B) is the compound difenoconazole; and component (C) is the compound chlorothalonil.
In one embodiment of the invention component (A) is a crystalline polymorph (form C) of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate as defined herein, component
(B) is the compound difenoconazole; and component (C) is the compound cyproconazole.
Components (B) and (C) in combination with component (A) may enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the fungicidal compositions may be effective against a wider spectrum of fungal pathogens that can be combated with the individual active ingredients when used solely.
Generally, the weight ratio of component (A) to the mixture of components (B) and (C) may be from 100:1 to 1 :100, or 50:1 to 1 :50, or 20:1 to 1 :20, or 10:1 to 1 :10, or 5:1 and 1 :5. Otherwise, the weight ratio of component (A) to the mixture of components (B) and (C) may be from 2:1 to 1 :2, or 4:1 to 2:1 , or 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.
In embodiments of the invention where the composition comprise a component (A), a component (B) and a component (C), the weight ratio of component (A) to the sum of component (B) and component
(C) may be from 100:1 to 1 :100, preferably from 50:1 to 1 :50, more preferably from 20:1 to 1 :40, even more preferably from 15:1 to 1 :30, still more preferably from 12:1 to 1 :25, or from 10:1 to 1 :20, or from 10:1 to 1 :10, or from 5:1 and 1 :15, or from 5:1 to 1 :5, or from 4:1 to 1 :4, or from 3:1 to 1 :10, or from 3:1 to 1 :3, or from 2:1 to 1 :5, or 1 :1 .
In one embodiment preferred fungicidal compositions used in the method of the invention comprising a mixture of components (A), (B) and (C) are disclosed in Table M3 to M34 below, wherein the term ‘Form A’ refers to a crystalline polymorph, form A of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate as defined herein. Table M3 - Specific Fungicidal Compositions
Figure imgf000090_0001
Figure imgf000091_0001
Table M4 - Specific Fungicidal Compositions
Figure imgf000091_0002
Figure imgf000092_0001
Table M5 - Specific Fungicidal Compositions
Figure imgf000093_0001
Figure imgf000094_0001
Table M6 - Specific Fungicidal Compositions
Figure imgf000094_0002
Figure imgf000095_0001
Table M7 - Specific Fungicidal Compositions
Figure imgf000095_0002
Figure imgf000096_0001
Figure imgf000097_0001
Table M8 - Specific Fungicidal Compositions
Figure imgf000097_0002
Figure imgf000098_0001
Table M9 - Specific Fungicidal Compositions
Figure imgf000098_0002
Figure imgf000099_0001
Table M10 - Specific Fungicidal Compositions
Figure imgf000099_0002
Figure imgf000100_0001
Figure imgf000101_0001
Table M11 - Specific Fungicidal Compositions
Figure imgf000101_0002
Figure imgf000102_0001
Table M12 - Specific Fungicidal Compositions
Figure imgf000102_0002
Figure imgf000103_0001
Table M13 - Specific Fungicidal Compositions
Figure imgf000103_0002
Figure imgf000104_0001
Table M14 - Specific Fungicidal Compositions
Figure imgf000105_0001
Figure imgf000106_0001
Table M15 - Specific Fungicidal Compositions
Figure imgf000106_0002
Figure imgf000107_0001
Table M16 - Specific Fungicidal Compositions
Figure imgf000107_0002
Figure imgf000108_0001
Table M17 - Specific Fungicidal Compositions
Figure imgf000108_0002
Figure imgf000109_0001
Table M18 - Specific Fungicidal Compositions
Figure imgf000109_0002
Figure imgf000110_0001
Table M19 - Specific Fungicidal Compositions
Figure imgf000111_0001
Table M20 - Specific Fungicidal Compositions
Figure imgf000112_0001
Table M21 - Specific Fungicidal Compositions
Figure imgf000113_0001
Table M22 - Specific Fungicidal Compositions
Figure imgf000114_0001
Table M23 - Specific Fungicidal Compositions
Figure imgf000115_0001
Table M24 - Specific Fungicidal Compositions
Figure imgf000115_0002
Figure imgf000116_0001
Table M25 - Specific Fungicidal Compositions
Figure imgf000116_0002
Figure imgf000117_0001
Table M26 - Specific Fungicidal Compositions
Figure imgf000117_0002
Figure imgf000118_0001
Table M27 - Specific Fungicidal Compositions
Figure imgf000118_0002
Figure imgf000119_0001
Table M28 - Specific Fungicidal Compositions
Figure imgf000119_0002
Figure imgf000120_0001
Table M29 - Specific Fungicidal Compositions
Figure imgf000120_0002
Figure imgf000121_0001
Table M30 - Specific Fungicidal Compositions
Figure imgf000121_0002
Figure imgf000122_0001
Table M31 - Specific Fungicidal Compositions
Figure imgf000122_0002
Table M32 - Specific Fungicidal Compositions
Figure imgf000122_0003
Figure imgf000123_0001
Table M33 - Specific Fungicidal Compositions
Figure imgf000123_0002
Figure imgf000124_0001
Table M34 - Specific Fungicidal Compositions
Figure imgf000124_0002
Figure imgf000125_0001
Figure imgf000126_0001
In a preferred embodiment of the invention there is provided a method of controlling or preventing infestation by phytopathogenic fungi (preferably, Phakopsora pachyrhizi) in a plant (preferably, soybean), wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qo inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein the composition is a composition selected from the group consisting of M1.001 to M34.012 (as disclosed in Tables M1 to M34). Preferably, in this embodiment of the invention the preferred weight ratio of component A:B is as disclosed in tables R1 and R2.
Further according to the invention, there is provided a method of controlling or preventing phytopathogenic fungi, especially Corynespora cassiicola, on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
Further according to the invention, there is provided a method of controlling or preventing phytopathogenic fungi, especially Phakopsora (including Phakopsora ampelopsidis and Phakopsora pachyrhizi), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
Further according to the invention, there is provided a method of controlling or preventing Phakopsora pachyrhizi, on useful plants (preferably, soybean) or on propagation material thereof, wherein said Phakopsora pachyrhizi comprises at least one of a F120L, Y131 F/H, K142R, I145F or I475T mutation in the CYP51 gene which confers resistance to sterol demethylation-inhibitors (DMI), said method comprising applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
Further according to the invention, there is provided a method of controlling or preventing phytopathogenic fungi, especially Cercospora (including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf. flagellaris, Cercospora janseana, Cercospora kikuchii, Cercospora lagenariae, Cercospora sojinae, Cercospora sorghi and Cercospora zeae-maydis), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
Furthermore, according to the invention, there is provided a method of controlling or preventing Cercospora (including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf. flagellaris, Cercospora janseana, Cercospora kikuchii, Cercospora lagenariae, Cercospora sojinae, Cercospora sorghi and Cercospora zeae-maydis), on useful plants (preferably, soybean) or on propagation material thereof, wherein said Cercospora comprises a G143A mutation in the mitochondrial cytochrome b which confers resistance to Qo inhibitors, said method comprising applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
Further according to the invention, there is provided a method of controlling or preventing Cercospora (including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf. flagellaris, Cercospora janseana, Cercospora kikuchii, Cercospora lagenariae, Cercospora sojinae, Cercospora sorghi and Cercospora zeae-maydis), on useful plants (preferably, soybean) or on propagation material thereof, wherein said Cercospora comprises at least one of a E297K, I330T or P384S mutation in the CYP51 gene which confers resistance to sterol demethylation-inhibitors (DMI), said method comprising applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
Further according to the invention, there is provided a method of controlling or preventing phytopathogenic fungi, especially Colletotrichum (including Colletotrichum acutatum, Colletotrichum cereale, Colletotrichum chrysanthemi, Colletotrichum cliviicola, Colletotrichum coccodes, Colletotrichum fragariae, Colletotrichum gloeosporioides, Colletotrichum graminicola, Colletotrichum lentis, Colletotrichum lindemuthianum, Colletotrichum musae, Colletotrichum orbiculare, Colletotrichum siamense and Colletotrichum truncatum), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
Further according to the invention, there is provided a method of controlling or preventing phytopathogenic fungi, especially Sclerotinia (including Sclerotinia minor, Sclerotinia borealis and Sclerotinia sclerotiorum), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34). Further according to the invention, there is provided a method of controlling or preventing Sclerotinia sclerotiorum, on useful plants (preferably, soybean) or on propagation material thereof, wherein said Sclerotinia sclerotiorum comprises at least one of a H273Y mutation in the SDH subunit B, or a H146R mutation in the SDH subunit C, or a H132R mutation in the SDH subunit D which confers resistance to succinate dehydrogenase inhibitors (SDHI), said method comprising applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1.001 to M34.012 (as disclosed in Tables M1 to M34).
Further according to the invention, there is provided a method of controlling or preventing phytopathogenic fungi, especially Septoria (including Septoria apiicola, Septoria glycines and Septoria lycopersici), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
Further according to the invention, there is provided a method of controlling or preventing phytopathogenic fungi, especially Peronospora (including Peronospora destructor, Peronospora farinosa f. sp. spinaciae and Peronospora viciae f. sp. Pisi), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
Further according to the invention, there is provided a method of controlling or preventing phytopathogenic fungi, especially Diaporthe (including Diaporthe amygdali, Diaporthe helianthin, Diaporthe neoviticola and Diaporthe phaseolorurri), on useful plants (preferably, soybean) or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a fungicidal composition, wherein the composition is a composition selected from the group consisting of M1 .001 to M34.012 (as disclosed in Tables M1 to M34).
The mixtures comprising a polymorph according to the invention, and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the polymorph according to the invention and the active ingredient(s) as described above, is not essential for working the present invention.
Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1g of active substance per kg of seeds. When the combinations of the present invention are used for treating seed, rates of 0.001 to 50 g of a compound of a polymorph per kg of seed, preferably from 0.01 to 10g per kg of seed are generally sufficient.
Suitably, a composition comprising a polymorph according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.
In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of a polymorph according to the invention optionally together with other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline: compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
Preferred formulations can have the following compositions (weight %):
Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %
Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The present invention will now be described by way of the following non-limiting examples and figures, wherein:
FIG. 1 shows the measured powder X-ray diffraction pattern of the polymorph form A of the invention. FIG. 2 shows the measured powder X-ray diffraction pattern of the polymorph form B of the invention. FIG. 3 shows the predicted powder X-ray diffraction pattern of the polymorph form C of the invention. FIG. 4 shows a DSC trace of the polymorph form A of the invention.
FIG. 5 shows a DSC trace of the polymorph form B of the invention.
FIG. 6 shows the predicted ideal solubility (as a solubility vs. temperature plot) of polymorphs form A and form B of the invention
EXAMPLES
1 . Preparation of Polymorphs - Form A (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate was made according to the methods described in WO 2022/200579.
The polymorph of the invention was made by adding ethanol to (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)- 3-methoxy-prop-2-enoate and left to stir for at least 30 minutes to ensure dissolution. The sample was then allowed to undergo evaporative crystallisation. The resulting crystals were ground using a pestle and mortar and X-ray diffraction analysis (PXRD) confirmed the presence of the polymorph, form A, of the invention.
2. Preparation of Polymorphs - Form B (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate was made according to the methods described in WG2020/193387.
The polymorph of the invention was made by purifying (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3- methoxy-prop-2-enoate by flash chromatography with Ethyl acetate/Cyclohexane solution resulting in the crystals nucleating. X-ray diffraction analysis (PXRD) confirmed the presence of the polymorph, form B, of the invention.
3. Preparation of Polymorphs - Form C
The compound of formula I was made according to the methods described in WO 2022/200579.
The polymorph of the invention was made by adding dimethyl carbonate to (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate and left to stir for at least 30 minutes to ensure dissolution. The sample was then allowed to undergo evaporative crystallisation. A single crystal was then analysed by X-ray diffraction (SCXRD) at 100 K (-173 °C) confirmed the presence of the polymorph, form C, of the invention.
Analysis of polymorphs
After preparation by the methods detailed above, the samples were subject to analysis by powder X-ray diffraction (PXRD) and/or single crystal X-ray diffraction (SCXRD) and/or differential scanning calorimetry (DSC).
Powder X-ray diffraction analysis of solid material was carried out using the Malvern Panalytical Empyrean powder X-ray diffractometer at room temperature. Samples were ground using a marble pestle and mortar for 4 minutes and packed onto a zero-background silicon wafer disc and the surface of the sample levelled with a microscope slide. The pXRD holder was placed in the instrument, spun (rotation time: 2s) and the powder pattern collected from 3.0° to 40° 2-theta with 0.0167° step size and 23s exposure time.
Measured powder X-ray diffraction patterns for the polymorphs of the invention form A and form B are shown in FIG. 1 and FIG. 2, respectively.
Single crystal intensity data was collected using a Rigaku SCXRD using a SuperNova (Cu Ka) X-ray source (wavelength: 1 .54184A) and a AtlasS2 area detector at room temperature and 100K. The data was solved using the CRYSTALS software package. This data was used to produce a predicted powder X-ray diffraction pattern for the polymorph, form C, of the invention (FIG. 3).
Differential scanning calorimetry (DSC) was carried out using the Waters TA-Discovery DSC 2500. 1- 5 mg of sample was weighed into the DSC aluminium crucible, the crucible was sealed using a hermetic lid and percid the sample then was analysed. The temperature profile for the analysis was 25-180°C at a heating rate of 10°C/min.
Although the invention has been described with reference to preferred embodiments and examples thereof, the scope of the present invention is not limited only to those described embodiments. As will be apparent to persons skilled in the art, modifications and adaptations to the above-described invention can be made without departing from the spirit and scope of the invention, which is defined and circumscribed by the appended claims. All publications cited herein are hereby incorporated by reference in their entirety for all purposes to the same extent as if each individual publication were specifically and individually indicated to be so incorporated by reference.

Claims

CLAIMS:
1 . A crystalline polymorph, form A of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)- 3-methoxy-prop-2-enoate, wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.0° ± 0.2°, 18.6° ± 0.2°, 20.3° ± 0.2° and 22.0° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
2. The crystalline polymorph according to claim 1 , wherein the polymorph further exhibits peaks at 16.5° ± 0.2°, 18.2° ± 0.2°, 23.5° ± 0.2°, 24.7° ± 0.2° and 26.6° ± 0.2° 20.
3. The crystalline polymorph according to claim 2, wherein the polymorph further exhibits peaks at 14.9° ± 0.2°, 16.9° ± 0.2°, 17.7° ± 0.2°, 21 .5° ± 0.2°, 21 .8° ± 0.2°, 24.5° ± 0.2° and 27.4° ± 0.2° 20.
4. The crystalline polymorph according to any one of claims 1 to 3, wherein the polymorph exhibits an X-ray diffraction pattern substantially as shown in Figure 1 .
5. The crystalline polymorph according to any one of claims 1 to 4, wherein the polymorph has the following lattice parameters: a = 12.7 A ± 0.1 , b = 11 .0 A ± 0.1 , c = 13.1 A ± 0.1 , a = 90.0° ± 0.1 °, p = 110.2° ± 0.1 °, y = 90.0°± 0.1 ° and volume = 1706.6 A3 ± 1 A3.
6. A crystalline polymorph, form B of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)- 3-methoxy-prop-2-enoate, wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.2° ± 0.2°, 18.7° ± 0.2°, 20.4° ± 0.2° and 24.4° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .5406 A.
7. The crystalline polymorph according to claim 6, wherein the polymorph further exhibits peaks at 8.4° ± 0.2°, 10.2° ± 0.2°, 18.5° ± 0.2°, 22.1 ° ± 0.2°, 22.9° ± 0.2°, 23.7° ± 0.2° and 24.9° ± 0.2° 20.
8. The crystalline polymorph according to claim 7, wherein the polymorph further exhibits peaks at 15.9° ± 0.2°, 17.4° ± 0.2°, 18.2° ± 0.2°, 23.3° ± 0.2° and 27.6° ± 0.2° 20.
9. The crystalline polymorph according to any one of claims 6 to 8, wherein the polymorph exhibits an X-ray diffraction pattern substantially as shown in Figure 2.
10. A crystalline polymorph, form C of the compound methyl (Z)-2-(5-cyclohexyl-2-methyl- phenoxy)-3-methoxy-prop-2-enoate, wherein the polymorph has an X-ray diffraction pattern comprising peaks at 12.1 ° ± 0.2°, 19.5° ± 0.2°, 20.7° ± 0.2° and 22.3° ± 0.2° 20 as measured by X-ray diffraction using an X-ray wavelength of 1 .54184 A.
11. The crystalline polymorph according to claim 10, wherein the polymorph further exhibits peaks at 8.9° ± 0.2°, 16.4° ± 0.2°, 17.6° ± 0.2°, 18.1 ° ± 0.2°, 21.4° ± 0.2°, 24.9° ± 0.2° and 25.0° ± 0.2° 20.
12. The crystalline polymorph according to claim 11 , wherein the polymorph further exhibits peaks at 15.7° ± 0.2°, 24.3° ± 0.2°, 26.5° ± 0.2°, 27.6° ± 0.2°, 28.1 ° ± 0.2° 20 and 28.6° ± 0.2° 20.
13. An agrochemical composition comprising a polymorph according to any one of claims 1 to 12 and an agrochemically acceptable carrier or diluent and optionally at least one additional active ingredient.
14. A method of controlling or preventing infestation by phytopathogenic fungi in a plant, wherein a fungicidally effective amount of a polymorph according to any of claims 1 to 12, or a composition comprising said polymorph as active ingredient, is applied to the plants, to parts thereof or the locus thereof.
15. The method of according to claim 14, wherein said phytopathogenic fungi comprises a F129L mutation in the mitochondrial cytochrome b which confers resistance to Qol inhibitors, said method comprising applying to the plant, to parts thereof or the locus thereof, a polymorph according to any of claims 1 to 12, or a composition comprising said polymorph as active ingredient.
PCT/EP2024/084896 2023-12-08 2024-12-05 Polymorphs of a methoxyacrylate derivative Pending WO2025120070A1 (en)

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