Solid agrochemical formulations comprising crystalline form a of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one

Abstract

NOT VISIBLE DUE TO STATUS OF PATENT

Description

[0001] Solid Agrochemical formulations comprising crystalline form A of 4-l(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino1furan-2(5H)-one

[0002] Summary of the invention

[0003] The present invention relates to a novel solid agrochemical formulations comprising a novel crystalline form of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one according to formula (1) which is the polymorphic form A, to a process for its preparation and to the novel crystalline form itself, as well as to its use for the production of agrochemical formulations and to its use in plant protection applications, especially to its use as an insecticide. The compound of the formula (1) which has the common name flupyradifurone and the lUPAC-name 4- [(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one and a process for its production is known from WO-A-2007 / 115644. A process for its preparation is also known from WO-A-2009 / 036899.

[0004] An amorphous and a crystalline form of the compound of formula (I) are already known from WO-A- 2011 / 051151. The crystalline form disclosed in WO-A-2011 / 051151 has been marked therein as being thermodynamic stable and has been characterized in that its X-ray powder diffractogram has as characteristic signals at 25°C and with Cu-Ka radiation (1.540598 A) being used at least 3 of the 20 (2 theta) values below:

[0005] The crystalline form disclosed in WO-A-2011 / 051151 is the polymorphic form B. The task of the present invention was to provide a solid formulation with the new polymorphic form A. The quality of a solid formulation, regarding processability, stability as well as biological performance, will strongly depend on the physicochemical properties of the active ingredient.

[0006] Background

[0007] Polymorphism is the ability of a compound to crystallize in different crystalline phases with different arrangements and / or conformations of the molecules in the crystal lattice. Hence, polymorphs are different crystalline forms of the same pure chemical compound. On account of the different arrangement and / or conformation of molecules, polymorphs exhibit different physical, chemical and biological properties. Properties which may be affected include but are not limited to solubility, dissolution rate, stability, optical and mechanical properties, etc. The relative stability of a polymorph depends on its free energy, i.e. a more stable polymorph has a lower free energy. Under a defined set of experimental conditions only one polymorph has the lowest free energy. This polymorph is the thermodynamically stable form and all other polymorph(s) is (are) termed metastable form(s). A metastable form is one that is thermodynamically unstable but can nevertheless be prepared, isolated and analyzed as a result of its relatively slow rate of transformation.

[0008] The occurrence of active substances in different polymorphic forms (hereinafter also named as polymorphs or crystalline forms) is of decisive importance for the production in industrial scale as well as for the development of formulations containing the active substance, as unwanted phase changes can lead to thickening and potentially solidification of the formulation and / or large crystals, which can lead to blockages in application equipment, e.g. in spray nozzles in agricultural application machinery. The knowledge of the existence of crystalline modifications and their properties is thus of high relevance. Each polymorph is characterized by a specific, uniform packing and arrangement of the molecules in the solid state. Nevertheless, it is generally not predictable whether a given chemical compound forms polymorphs at all and if so, which physical and biological properties the different polymorphs may have.

[0009] In addition, pseudopolymophic forms, named hydrates or solvates, can occur. A solvate is a crystalline molecular compound in which molecules of the solvent of crystallisation are incorporated into the host lattice, consisting of unsolvated molecules. A hydrate is a special case of a solvate when the incorporated solvent is water. The presence of solvent molecules in the crystal lattice influences the intermolecular interactions and confers unique physical properties to each solvate. A solvate thus has its own characteristic values of internal energy, enthalpy, entropy, Gibbs free energy, and thermodynamic activity. Figures

[0010] Fig. la: X-ray powder diffractogram of polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one

[0011] Fig. lb: FT Raman spectrum of polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one

[0012] Fig. 1c: IR spectrum of polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one

[0013] Fig. Id: DSC thermogram of polymorphic form A

[0014] Fig. 2a: X-ray powder diffractogram of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one

[0015] Fig. 2b: FT Raman spectrum of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one

[0016] Fig. 2c: IR spectrum of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one

[0017] Fig. 2d: DSC thermogram of polymorphic form B

[0018] Detailed description

[0019] As pointed out above, one embodiment of the present invention relates to a novel crystalline form A of 4- [(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one according to formula (1), which hereinafter is also termed as flupyradifurone (FPF).

[0020] Surprisingly a new polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan- 2(5H)-one of formula (1) has been found which is the thermodynamic stable form and which shows improved properties compared to the polymorphic form B disclosed in WO-A-2011 / 051151 which has been found to be only metastable although it is kinetically quite stable. Polymorph A of flupyradifurone as such and liquid formulations containing this form are described in WO 2023 / 237444. However, no solid compositions are described therein.

[0021] EP4265110 discloses water dispersible granules containing flupyradifurone, but gives no disclosure about the polymorphic form A of flupyradifurone.

[0022] In particular, it was now surprisingly found that the new solid formulation according to the invention of the polymorphic form A has improved or comparable storage stability at elevated temperatures among others due to a significant increase of the melting point.

[0023] Moreover, water solubility of form A is significantly lower than that of form B. A lower water solubility of the active ingredient would normally result in a lower efficacy at the same concentration. Hence one would expect that a higher amount of form A would have to be used to achieve the same efficacy as for form B. This would be unfavourable in view of economical and also ecological aspects. However, despite the lower solubility it has surprisingly been found that the biological activity / efficacy, in particular in the formulations according to the instant invention containing compound A, is not reduced.

[0024] The compound 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one contains hydrogen atoms at various positions which may be any hydrogen isotope, i.e. ’H or2H (deuterium). Thus, the compound 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one may contain no, one or more than one deuterium atom. In a preferred embodiment, the compound 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one contains hydrogen in its natural abundance isotopic composition, i.e. about 0.015 % deuterium (molar ratio).

[0025] The polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by X-ray powder diffractometry on the basis of the respective diffraction diagrams, which are recorded at 25°C and with Cu-Ka 1 radiation (1.5406 A). The polymorphic form A according to the present invention displays at least 3, often at least 5, in particular at least 7, more particularly at least 10, and especially all of the reflections quoted in the following as values:

[0026] Table 1: X-ray reflections of polymorphic form A

[0027] The polymorphic form A according to the present invention is further characterized by the X-ray powder diffractogram depicted in Fig. [la]. In a preferred embodiment the polymorphic form A according to the present invention displays at least 3, in particular at least 5, and especially all of the following characteristic reflections quoted as 20 value + 0.2°: 15,0; 20,1; 21,0; 22,4; 29,4; 33,1 and 33,2. In one embodiment the polymorphic form A according to the present invention displays at least the following characteristic reflections quoted as 20 value: 21,0; 22,4 and 29,4.

[0028] In one embodiment the polymorphic form A according to the present invention displays at least the following characteristic reflections quoted as 20 value: 15,0; 20,1; 21,0; 22,4 and 29,4. In one embodiment the polymorphic form A according to the present invention displays at least the following characteristic reflections quoted as 20 value: 15,0; 20,1; 21,0; 22,4; 29,4; 33,1 and 33,2.

[0029] The polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by Raman spectroscopy on the basis of the respective spectrum, which are recorded at 25 °C and with a laser wavelength of 1064 nm and a resolution of 2 cm ’.The polymorphic form A according to the present invention displays at least 3, often at least 5, in particular at least 7, and especially all of the bands quoted in the following as peak maxima:

[0030] Table 2: Raman bands of form A

[0031] The polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by infrared spectroscopy on the basis of the respective spectrum, which are recorded at 25 °C using an universal diamond ATR device and a resolution of 2 cm1. The polymorphic form A according to the present invention displays at least 3, often at least 5, in particular at least 7, and especially all of the bands quoted in the following as peak maxima:

[0032] Table 3: IR bands of form A

[0033] In addition to the polymorphic form A, polymorphic form B is known from WO-A-2011 / 051151, which is further characterized in the following.

[0034] The polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by X-ray powder diffractometry on the basis of the respective diffraction diagrams, which are recorded at 25°C and with Cu-Ka 1 radiation (1.5406 A). The polymorphic form B displays at least 3, often at least 5, in particular at least 7, more particularly at least 10, and especially all of the reflections quoted in the following as values:

[0035] Table 4: X-ray reflections of polymorphic form B

[0036] The polymorphic forms B are further characterized by the X-ray powder diffractograms depicted in Fig. [2a].

[0037] The polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by Raman spectroscopy on the basis of the respective spectrum, which are recorded at 25 °C and with a laser wavelength of 1064 nm and a resolution of 2 cm ’.The polymorphic form B displays at least 3, often at least 5, in particular at least 7, and especially all of the bands quoted in the following as peak maxima:

[0038] Table 5: Raman bands of form B

[0039]

[0040] The polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by infrared spectroscopy on the basis of the respective spectrum, which are recorded at 25 °C using an universal diamond ATR device and a resolution of 2 cm1. The polymorphic form B displays at least 3, often at least 5, in particular at least 7, and especially all of the bands quoted in the following as peak maxima:

[0041] Table 6: IR bands of form B

[0042] Embodiment for production of form A

[0043] In another embodiment, the present invention is directed to a process for the production of the polymorphic form A, comprising the following steps: a) diluting and / or suspending the compound of formula (1) in a suitable solvent or solvent mixture; b) adjusting a temperature of between 0 and 25°C optionally by heating or cooling the same; and c) storing the solution or slurry obtained in step b) at a temperature of between 0 and 25 °C until the solvent is evaporated and crystals of polymorphic form A have formed.

[0044] The chemical preparation of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one according to formula (1) in known from the prior art such WO-A-2007 / 115644 or WO-A-2009 / 036899. The compound of formula (1) as used in step a) can thus be prepared according to WO-A-2007 / 115644 or WO-A-2009 / 036899 to which full reference is made hereby. Preferably the chemical preparation of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan- 2(5H)-one is performed according to WO-A-2007 / 115644 with butyronitrile as a solvent. The crystallization and filtration of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one is preferably performed in butanol. After filtration the crystals obtained are preferably washed with ethanol.

[0045] The compound of formula (1) in step a) can essentially be any known form of 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one. This means that 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be used in amorphous form or in a mixture of different polymorphic forms or in a mixture containing an amorphous and one or more different polymorphic forms.

[0046] Suitable solvents or solvent mixtures which can be used to dilute and / or suspend the compound of formula (1) in step a) and from which the compound of formula (1) is obtained in polymorphic form A in step c), are any suitable solvent such as aromatic solvents or alcohols or esters or water, preferably toluene, methanol, ethanol, butanol, ethyl acetate, isopropanol or water.

[0047] The solution of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can also be prepared by transferring a reaction mixture obtained by chemical reaction, containing 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, if necessary after removal of reagents and / or side products into a solvent or solvent mixture according to the present invention.

[0048] In step b) the temperature of the solution or slurry is adjusted to a temperature of 0°C to 25°C. This can be done by cooling or heating or by waiting until the temperature has adjusted to the room temperature (if it is between 0°C and 25°C).

[0049] In step c) the solution or slurry obtained in step b) is stored at a temperature of between 0 and 25 °C until the solvent is evaporated and crystals of polymorphic form A have formed. Preferably, the polymorphic form A is isolated from the solvent or solvent mixture by allowing the solution or slurry to stand at the crystallization conditions of step c) until at least 90 wt.-% of the solvent or solvent mixture is evaporated.

[0050] The crystallization of polymorphic form A can be promoted or accelerated by seeding with seed crystals of form A.

[0051] The isolation of the polymorphic form A from the mother liquid is effected by common techniques known in the art, for example by filtration, centrifugation or by decanting.

[0052] The isolated polymorphic form A can optionally be washed with any solvent, preferably with the solvent or solvent mixture used for crystallization, with water or with a mixture of the solvent or solvent mixture and water. The washing step can optionally be repeated, whereby washing with water often is the last washing step. The washing is typically performed at temperatures below 30°C, often below 25°C and in particular below 20°C, optionally at 0 °C. In a further, optionally step, the crystals of polymorphic form A can be dried and then supplied for further processing.

[0053] By means of the crystallization according to the present invention, form A of 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one is obtained with at least 85 %, in particular 90 %, and most preferably at least >95 %.

[0054] This means, that apart from other possible impurities, preferably the amount of remaining form B or amorphous forms is < 15 %, in particular < 10%, and most preferably < 5%.

[0055] The content of form A according to the present invention is analyzed by IR spectroscopy. Based on calculated electronically mixed IR spectra (mixed by a software calculator in 5 % steps) a calibration curve, using a PLS regression, is generated. With this curve the proportional shares of the different forms are calculated. Due to the calibration accuracy the content of 100 % of polymorphic form A is not excluded by the above wording.

[0056] Thus, a particular embodiment of the present invention relates to 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one which consists of at least 85% and often at least 90 % or at least >95 % of the polymorphic form A.

[0057] Another, alternative embodiment of the present invention is the process for the preparation of aqueous dispersions of Flupyradifurone, whereby the form of Flupyradifurone can be steered / controlled as a function of the milling parameters. The relative amount of form A in mixtures of form B and form A of Flupyradifurone can be maintained or increased depending on the milling parameters (see Table 11).

[0058] The choice of grinding media during the milling process is known to affect the energy input during milling (Austin, L.G., Klimpel, R.R. and Luckie, P.T., 1984. Process engineering of size reduction: ball milling. Society of Mining Engineers of the AIME), so that denser grinding media (e.g. Zirconium Oxide beads) induce higher energy this resulting in, amongst other effects, an increase of the exit temperature of the mill base, a potential lowering of the viscosity of the mill base, this causing a direct increase in the milling efficiency. We have observed that under these conditions the relative amount of Flupyradifurone form A can be increased from a low amount to form A being the major component in the mixture.

[0059] On the contrary, the use of less dense grinding media material (e.g. glass beads) does not affect the temperature of the milling process, and as such within the limits of analytical detection form A does not increase during milling with glass beads at room temperature. Embodiment for agrochemical formulations with form A

[0060] In another embodiment, the present invention is directed to a plant protection agent in the form of customary formulations (agrochemical formulations) containing the polymorphic form A of 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one wherein at least 85 % by weight (preferably at least 90 % by weight and more preferably at least 95 % by weight) of the compound of formula (1) is present in its crystalline form A. The remaining less than 15 % by weight (preferably less than 10% by weight, more preferably less than 5 % by weight) contains other polymorphic forms of the compound of formula (I)) such as the amorphous or the crystalline form disclosed in WO-A-2011 / 051151 (form B).

[0061] For the avoidance of doubt the term at least 85 % by weight or at least 90 % by weight or at least 95 % by weight means 85 - 100 % by weight or 90 - 100 % by weight or 95 - 100 % by weight.

[0062] Formulation types

[0063] Customary formulations (agrochemical formulations) are, for example, water-soluble liquids (SE), emulsion concentrates (EC), emulsions in water (EW), suspension concentrates (SC, SE, FS, OD), water- dispersible granules (WG), granules (GR) and capsule concentrates (CS); these and further possible formulation types are described, for example, by Crop Life International and in Pesticide Specifications, Manual on development and use of FAO and WHO specifications for pesticides, FAO Plant Production and Protection Papers - 173, prepared by the FAO / WHO Joint Meeting on Pesticide Specifications, 2004, ISBN: 9251048576.

[0064] Preference is given to formulations or use forms comprising auxiliaries, for example extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, frost protection agents, biocides, thickeners and / or further auxiliaries, for example adjuvants. An adjuvant in this context is a component which enhances the biological effect of the formulation, without the component itself having any biological effect. Examples of adjuvants are agents which promote retention, spreading, attachment to the leaf surface or penetration.

[0065] The composition of the invention may be provided to the end user as ready-for-use formulation, i.e. the compositions may be directly applied to the plants or seeds by a suitable device, such as a spraying or dusting device. Alternatively, the compositions may be provided to the end user in the form of concentrates which have to be diluted, preferably with water, prior to use.

[0066] These formulations are prepared in a known way, for example by mixing the compounds of the formula (I) with auxiliaries such as, for example, extenders, solvents and / or solid carriers and / or other auxiliaries such as, for example, surfactants. The formulations are produced either in suitable facilities or else before or during application. The composition of the invention may be powders (e.g. wettable powders, soluble powders), dusts, pastes, granules (e.g. soluble granules, granules for broadcasting). The compound combination of the invention may be present inwettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG). These and further compositions types are defined by the Food and Agriculture Organization of the United Nations (FAO). An overview is given in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 7th Ed. March 2017, Croplife International.

[0067] The object of the invention was to provide a formulation with a high loading of active ingredient in which other actives could easily be integrated, which exhibit good storage stability, in particular at higher temperatures, which show at least a comparable bioefficacy to formulations known in the prior art (polymorph Form B; e.g. PCT / EP20237059974, WO2019 / 197631, PCT / EP2023 / 068582)

[0068] Hence, preference is given to formulations in form of granules (e.g. WG, SG, GR, FG, GG, MG), wherein WG and SG formulations are preferred. The quality of a solid formulation, regarding processability, stability, solubility / redispersibility as well as biological performance, will strongly depend on the physicochemical properties of the active ingredient and might negatively influence if exchanged in a formulation.

[0069] These formulations are prepared in a known manner, by mixing form A (polymorph form A) of the compounds of the formula (I) with customary additives such as, for example, customary extenders and also solvents or diluents, colorants, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins and also water and processed as needed.

[0070] Surprisingly, it was found that novel formulations according to the instant invention of Flupyradifurone using polymorph form A did also show good processability and excellent physical properties (stability, solubility, redispersibility) of the formulation. Moreover, surprisingly it was found that, although polymorph form A has significant lower water solubility than form B, biological efficacy using either granules containing polymorph form A or B was identical independent of the used product amounts and water amounts for the spray solutions.

[0071] Formulation of the present invention

[0072] The formulations according to the invention are exemplified as shown below:

[0073] In one preferred embodiment the agrochemical formulation comprises a) the polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one wherein at least 85 % by weight (preferably at least 90 % by weight and more preferably at least 95 % by weight) of the compound of formula (1) is present in its crystalline form A.

[0074] The remaining less than 15 % by weight (preferably less than 10% by weight, more preferably less than 5 % by weight) contains other polymorphic forms of the compound of formula (I)) such as the amorphous or the crystalline form disclosed in WO-A-2011 / 051151.

[0075] For the avoidance of doubt the term at least 85 % by weight or at least 90 % by weight or at least 95 % by weight means 85 - 100 % by weight or 90 - 100 % by weight or 95 - 100 % by weight.

[0076] This definition is true for all references to polymorphic form A if not explicitly otherwise indicated in the instant invention.

[0077] In another preferred embodiment, the WG formulation comprises a) the polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one wherein at least 85 % by weight (preferably at least 90 % by weight and more preferably at least 95 % by weight) of the compound of formula (1) is present in its crystalline form A, b) optional other active ingredients, c) at least one dispersant, d) at least one water soluble filler, e) a water insoluble filler, f) at least one structure former and g) optional other common adjuvants or formulations aids

[0078] In a further preferred embodiment, one or more or all of compounds b) and g) are present, i.e. b, or g or b and g-

[0079] The plant protection formulation may additionally comprise one or more further active substance(s) (b) selected from the group consisting of herbicides, insecticides, acaricides, fungicides, safeners and / or plant growth regulator.

[0080] The active compounds identified here by their common names are known and are described, for example, in the pesticide handbook (“The Pesticide Manual” 16th Ed., British Crop Protection Council 2012) or can be found on the Internet (e.g. http: / / www.alanwood.net / pesticides). The classification is based on the current IRAC Mode of Action Classification Scheme at the time of filing of this patent application. In one preferred embodiment the one or more further active substance is selected from the group of insecticides / acaricides and nematicides.

[0081] Preferably those are selected from:

[0082] (1) Acetylcholinesterase (AChE) inhibitors, preferably carbamates selected from alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb, or organophosphates selected from acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon and vamidothion.

[0083] (2) GABA-gated chloride channel blockers, preferably cyclodiene-organochlorines selected from chlordane and endosulfan, or phenylpyrazoles (fiproles) selected from ethiprole and fipronil.

[0084] (3) Sodium channel modulators, preferably pyrethroids selected from acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(IR)-trans-isomer], deltamethrin, empenthrin [(EZ)-(lR)-isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(IR)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)- isomer)], tralomethrin and transfluthrin, or DDT or methoxychlor.

[0085] (4) Nicotinic acetylcholine receptor (nAChR) competitive modulators, preferably neonicotinoids selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam, or nicotine, or sulfoximines selected from sulfoxaflor, or butenolids selected from flupyradifurone, or mesoionics selected from triflumezopyrim.

[0086] (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators (Site I), preferably spinosyns selected from spinetoram and spinosad. (6) Glutamate-gated chloride channel (GluCl) allosteric modulators, preferably avermectins / milbemycins selected from abamectin, emamectin benzoate, lepimectin and milbemectin.

[0087] (7) Juvenile hormone mimics, preferably juvenile hormone analogues selected from hydroprene, kinoprene and methoprene, or fenoxycarb or pyriproxyfen.

[0088] (8) Miscellaneous non-specific (multi-site) inhibitors, preferably alkyl halides selected from methyl bromide and other alkyl halides, or chloropicrine or sulphuryl fluoride or borax or tartar emetic or methyl isocyanate generators selected from diazomet and metam.

[0089] (9) Chordotonal organ TRPV channel modulators, preferably pyridine azomethanes selected from pymetrozine and pyrifluquinazone, or pyropenes selected from afidopyropen.

[0090] (10) Mite growth inhibitors affecting CHS1 selected from clofentezine, hexythiazox, diflo vidazin and etoxazole.

[0091] (11) Microbial disruptors of the insect gut membranes selected from Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and B. t. plant proteins selected from Cry 1 Ab, Cry 1 Ac, CrylFa, Cry 1 A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb and Cry34Abl / 35Abl.

[0092] (12) Inhibitors of mitochondrial ATP synthase, preferably ATP disruptors selected from diafenthiuron, or organotin compounds selected from azocyclotin, cyhexatin and fenbutatin oxide, or propargite or tetradifon.

[0093] (13) Uncouplers of oxidative phosphorylation via disruption of the proton gradient selected from chlorfenapyr, DNOC and sulfluramid.

[0094] (14) Nicotinic acetylcholine receptor channel blockers selected from bensultap, cartap hydrochloride, thiocylam and thiosultap-sodium.

[0095] (15) Inhibitors of chitin biosynthesis affecting CHS1, preferably benzoylureas selected from bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.

[0096] (16) Inhibitors of chitin biosynthesis, type 1 selected from buprofezin.

[0097] (17) Moulting disruptor (in particular for Diptera, i.e. dipterans) selected from cyromazine.

[0098] (18) Ecdysone receptor agonists, preferably diacylhydrazines selected from chromafenozide, halofenozide, methoxyfenozide and tebufenozide. (19) Octopamine receptor agonists selected from amitraz.

[0099] (20) Mitochondrial complex III electron transport inhibitors selected from hydramethylnone, acequinocyl, fluacrypyrim and bifenazate.

[0100] (21) Mitochondrial complex I electron transport inhibitors, preferably METI acaricides and insecticides selected from fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad, or rotenone (Derris).

[0101] (22) Voltage-dependent sodium channel blockers, preferably oxadiazines selected from indoxacarb, or semicarbazones selected from metaflumizone.

[0102] (23) Inhibitors of acetyl CoA carboxylase, preferably tetronic and tetramic acid derivatives selected from spirodiclofen, spiromesifen, spiropidion and spirotetramat.

[0103] (24) Mitochondrial complex IV electron transport inhibitors, preferably phosphides selected from aluminium phosphide, calcium phosphide, phosphine and zinc phosphide, or cyanides selected from calcium cyanide, potassium cyanide and sodium cyanide.

[0104] (25) Mitochondrial complex II electron transport inhibitors, preferably / ?<?m-kctonitrilc derivatives selected from cyenopyrafen and cyflumetofen, or carboxanilides selected from pyflubumide.

[0105] (28) Ryanodine receptor modulators, preferably diamides selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide and tetraniliprole.

[0106] (29) Chordotonal organ Modulators (with undefined target site) selected from flonicamid.

[0107] (30) GABA-gated chlorid channel allosteric modulators, preferably meta-diamides selected from broflanilide, or isoxazoles selected from fluxametamide.

[0108] (31) Baculoviruses, preferably Granuloviruses (GVs) selected from Cydia pomonella GV and Thaumatotibia leucotreta (GV), or Nucleopolyhedro viruses (NPVs) selected from Anticarsia gemmatalis MNPV, Flucypyriprole and Helicoverpa armigera NPV.

[0109] (32) Nicotinic acetylcholine receptor allosteric modulators (Site II) selected from GS-omega / kappa HXTX-Hvla peptide.

[0110] (33) further active compounds selected from Acynonapyr, Afoxolaner, Azadirachtin, Benclothiaz, Benzoximate, Benzpyrimoxan, Bromopropylate, Chinomethionat, Chloroprallethrin, Cryolite, Cyclobutrifluram, Cycloxaprid, Cyetpyrafen, Cyhalodiamide, Cyproflanilide (CAS 2375110-88-4), Dicloromezotiaz, Dicofol, Dimpropyridaz, epsilon-Metofluthrin, epsilon-Momfluthrin, Flometoquin, Fluazaindolizine, Flucypyriprole (CAS 1771741-86-6), Fluensulfone, Flufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon, Fluopyram, Flupyrimin, Fluralaner, Fufenozide, Flupentiofenox, Guadipyr, Heptafluthrin, Imidaclothiz, Iprodione, Isocycloseram, kappa-Bifenthrin, kappa-Tefluthrin, Lotilaner, Meperfluthrin, Nicofluprole (CAS 1771741-86-6), Oxazosulfyl, Paichongding, Pyridalyl, Pyrifluquinazon, Pyriminostrobin, Sarolaner, Spidoxamat, Spirobudiclofen, Tetramethylfluthrin, Tetrachlorantraniliprole, Tigolaner, Tioxazafen, Thiofluoximate, Tyclopyrazoflor, lodomethane; furthermore preparations based on Bacillus firmus (1-1582, Votivo) and azadirachtin (BioNeem), and also the following compounds: l-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-3- (trifluoromethyl)-lH-l,2,4-triazole-5-amine (known from W02006 / 043635) (CAS 885026-50-6), 2- chloro-N-[2- { 1 -[(2E)-3-(4-chlorophenyl)prop-2-en- 1 -yl]piperidin-4-yl } -4- (trifluoromethyl)phenyl]isonicotinamide (known from W02006 / 003494) (CAS 872999-66-1), 3-(4- chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-l,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-l,8- diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP2647626) (CAS 1440516-42-6), PF1364 (known from JP2010 / 018586) (CAS 1204776-60-2), (3E)-3-[l-[(6-chloro-3-pyridyl)methyl]-2- pyridylidene]-l,l,l-trifluoro-propan-2-one (known from WO2013 / 144213) (CAS 1461743-15-6), A-[3- (benzylcarbamoyl)-4-chlorophenyl]-l-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-lH-pyrazole-5- carboxamide (known from WO2010 / 051926) (CAS 1226889-14-0), 5-bromo-4-chloro-A-[4-chloro-2- methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3- isoxazolyl]-2-methyl-A-(cA-l-oxido-3-thietanyl)-benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5- (trifhroromethyl)-3-isoxazolyl]-2-methyl-A-(tran.s-l-oxido-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5- dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-A-(cA-l-oxido-3-thietanyl) benzamide (known from WO 2013 / 050317 Al) (CAS 1332628-83-7), A-[3-chloro-l-(3-pyridinyl)-lH- pyrazol-4-yl]-A-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide, (+)-A-[3-chloro-l-(3-pyridinyl)- lH-pyrazol-4-yl]-A-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide and (-)-A-[3-chloro-l-(3- pyridinyl)-lH-pyrazol-4-yl]-A-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide (known from WO 2013 / 162715 A2, WO 2013 / 162716 A2, US 2014 / 0213448 Al) (CAS 1477923-37-7), 5-[[(2E)-3- chloro-2-propen- 1 -yl] amino] - 1 - [2,6-dichloro-4-(trifluoromethyl)phenyl] -4- [(trifluoromethyl)sulfinyl] - lH-pyrazole-3-carbonitrile (known from CN 101337937 A) (CAS 1105672-77-2), 3-bromo-A-[4-chloro- 2-methyl-6-[(methylamino)thioxomethyl]phenyl]-l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide, (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9); W[4-chloro-2-[[(l,l- dimethylethyl)amino]carbonyl]-6-methylphenyl]-l-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-l / 7- pyrazole-5-carboxamide (known from WO 2012 / 034403 Al) (CAS 1268277-22-0), A-[2-(5-amino-l ,3, 4-thiadiazol-2-yl)-4-chloro-6-methylphenyl] -3-bromo- 1 -(3-chloro-2-pyridinyl)- lH-pyrazole-5- carboxamide (known from WO 2011 / 085575 Al) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3- dichloro-2-propen-l-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN 101337940 A) (CAS 1108184-52-6); ( E)- and 2(Z)-2-[2-(4-cyanophenyl)-l-[3-(trifluoromethyl) phenyl] ethylidene] -N- [4-(difluoromethoxy)phenyl] -hydrazinecarboxamide (known from CN 101715774 A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(lH-benzimidazol-2- yl)phenyl-cyclopropanecarboxylic acid ester (known from CN 103524422 A) (CAS 1542271-46-4); (4aS) -7 -chloro-2,5 -dihydro-2- [ [(methoxycarbonyl) [4- [(trifluoromethyl)thio] phenyl] amino] carbonyl] - indeno[l,2-e][l,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN 102391261 A) (CAS 1370358-69-2); 6-deoxy-3-(9-ethyl-2,4-di-(9-methyl-, l-[A-[4-[l-[4-(l,l,2,2,2-pentafluoroethoxy) phenyl]-l H-l ,2,4-triazol-3-yl]phenyl]carbamate]-a-L-mannopyranose (known from

[0111] US 2014 / 0275503 Al) (CAS 1181213-14-8); 8-(2-cycIopropylmethoxy-4-trifluoromethyI-phenoxy)-3- (6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1 ]octane (CAS 1253850-56-4), (8-antz)-8-(2- cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza- bicyclo[3.2.1 ]octane (CAS 933798-27-7), (8-yyn)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy) -3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (known from WO 2007040280 Al, WO 2007040282 Al) (CAS 934001-66-8), N-[4-(aminothioxomethyl)-2-methyl-6-

[0112] [(methylamino)carbonyl]phenyl]-3-bromo-l-(3-chloro-2-pyridinyl)-l / 7-pyrazole-5-carboxamide (known from CN 103265527 A) (CAS 1452877-50-7), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-l-methyl- l,8-diazaspiro[4.5]decane-2, 4-dione (known from WO 2014 / 187846 Al) (CAS 1638765-58-8), 3-(4- chloro-2,6-dimethylphenyl)-8-methoxy-l-methyl-2-oxo-l,8-diazaspiro[4.5]dec-3-en-4-yl-carbonic acid ethyl ester (known from WO 2010 / 066780 Al, WO 2011151146 Al) (CAS 1229023-00-0), N-[l-(2,6- difluorophenyl)-lH-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO 2014 / 053450 Al) (CAS 1594624-87-9), N-[2-(2,6-difluorophenyl)-2H-l,2,3-triazol-4-yl]-2-(trifluoromethyl)benzamide (known from WO 2014 / 053450 Al) (CAS 1594637-65-6), N-[l-(3,5-difluoro-2-pyridinyl)-lH-pyrazol- 3-yl]-2-(trifluoromethyl)benzamide (known from WO 2014 / 053450 Al) (CAS 1594626-19-3), (31?)-3-(2- chloro-5-thiazolyl)-2,3-dihydro-8-methyl-5,7-dioxo-6-phenyl-5H-thiazolo[3,2-a]pyrimidinium inner salt (known from WO 2018 / 177970 Al) (CAS 2246757-58-2); 3-(2-chloro-5-thiazolyl)-2,3-dihydro-8- methyl-5,7-dioxo-6-phenyl-5H-thiazolo[3,2-a]pyrimidinium inner salt (known from WO 2018 / 177970 Al) (CAS 2246757-56-0); N-[3-chloro-l-(3-pyridinyl)-lH-pyrazol-4-yl]-2-(methylsulfonyl)- propanamide (known from WO 2019 / 236274 Al) (CAS 2396747-83-2), N-[2-bromo-4-[l,2,2,2- tetrafluoro- 1 -(trifluoromethyl)ethyl] -6-(trifluoromethyl)phenyl] -2-fluoro-3-[(4-fluorobenzoyl)amino] - benzamide (known from WO 2019059412 Al) (CAS 1207977-87-4), 3-Bromo-l-(3-chloro-2-pyridinyl)- N-[4,6-dichloro-3-fhioro-2-[(methylamino)carbonyl]phenyl]-lH-Pyrazole-5-carboxamide (Fluchlorodiamide; known from CN110835330 A, CN106977494 A) (CAS: 2129147-03-9).

[0113] In another preferred embodiment, said one or more further active substance is a fungicide.

[0114] In another preferred embodiment, said further active substance is a biological pesticide.

[0115] Biological pesticides comprise in particular bacteria, fungi, yeasts, plant extracts and products formed by microorganisms, including proteins and secondary metabolites.

[0116] Biological pesticides comprise bacteria such as spore-forming bacteria, root-colonising bacteria and bacteria which act as biological insecticides, fungicides or nematicides.

[0117] In another embodiment the compounds of the formula (I) can be combined with safeners.

[0118] All named mixing partners can, if their functional groups enable this, optionally form salts with suitable bases or acids. All named mixing partners can include tautomeric forms, where applicable.

[0119] Preferred mixing partners are selected from the group comprising beta-cyfluthrin, Deltamethrin, Permethrin, Transfluthrin, Spiromesifen, Spidoxamat, Ethiprole, Fipronil, Thiacloprid and Tetraniliprole.

[0120] Most preferred mixing partners are Spiromesifen and Spidoxamat. c) Dispersing agents

[0121] Suitable dispersants, which also can have wetting properties, in the context of the present invention are dispersants which are usually used for this purpose in solid agrochemical agents, wherein solid dispersants are preferred.

[0122] In general, suitable salts in the instant invention, if not otherwise indicated, are selected from the group of alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium or various amines.

[0123] Suitable dispersants according to the present invention are dispersants selected from the group of alkylnaphtyl sulfonates, lignin sulfonates and salts thereof, and polycarboxylates.

[0124] A further preferred group of dispersing aids are alkali metal, alkaline earth metal and ammonium salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of alkylnaphthalene sulphonic acids, salts of naphthalene-sulphonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid. Mono-and diesters of sulfosuccinate metal salts with branched or linear alcohols comprising 1-10 carbon atoms, in particular for the latter alkali metal salts, more particular sodium salts, and most particular sodium dioctylsulfosuccinate.

[0125] Moreover, dispersants according to the present invention are materials selected from the group of lignin sulfonates and salts thereof, preferably selected from the group of lignin sulfonates and salts thereof, for example Borresperse NA, Borresperse 3 A, Ultrazine NA, Ufoxane 3 A, Vanisperse CB, Marasperse AG, MARASPERSE N 22, MARASPERSE C 21, MARASPERSE CBOS-4, WAFEX CA122 und Borresperse CA der Fa. Borregaard; KRAFTSPERSE EDF-350, KRAFTSPERSE 25M, KRAFTSPERSE EDF-450, REAX 100M, REAX 83A, REAX 85A, REAX 88A, REAX 88B, REAX 907, REAX 910, POLYFON H, POLYFON O und POLYFON T (Ingevity); AGRINOL DN 19 und Agrinol C12 ( Fa. Tembec). Further suitable dispersants in the context of the present invention are dispersants of the polycarboxylate type, for example those such as hydrophobically modified comb-like polymers, for example polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, a copolymer of maleic acid or maleic anhydride with an olefin (such as isobutylene or diisobutylene), a copolymer of acrylic acid and itaconic acid, a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid or maleic anhydride and styrene, a copolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and methacrylate, a copolymer of acrylic acid and vinyl acetate, a copolymer of styrene and methacrylic acid, modified copolymers of styrene and methacrylic acid, a copolymer of maleic acid or maleic anhydride and acrylic acid, an N-methyl fatty acid (e.g. C8-C18)-sarcosinate, a carboxylic acid such as a resin acid or a fatty acid (e.g. C8-C18) or a salt of such a carboxylic acid.

[0126] Further preferred are dispersants from the group comprising sodium salts of the copolymers of maleic acid and olefins (e.g. Geropon T / 36 / Solvay; Duramax D-305 / Dow); and sodium salts of copolymers of (meth)acrylic acid and styrene (Tersperse 2700 / Indorama; Atlox Metasperse 500S / Croda).

[0127] Further useful nonionic dispersants include all substances of this type which are typically usable in agrochemical compositions. Preferably made of polyethylene oxide -polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and / or propylene oxide, and also polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic esters, and additionally alkyl ethoxylates and alkylaryl ethoxylates, which optionally may be phosphated and optionally may be neutralized with bases, mention being made, by way of example, of sorbitol ethoxylates, and, as well, polyoxyalkylenamine derivatives.

[0128] Suitable anionic dispersants include all substances of this type that can typically be used in agrochemical compositions.

[0129] Dispersing agents c) that are further preferred in the context of the present invention are dispersants selected from the group of the sodium salts of alkylated naphthalene sulfonates, for example ©Morwet EFW, and the sodium salts of dioctylsulfosuccinic acid, for example ©Aerosol OTB, and more preferably consisting of the sodium salts of alkylated naphthalene sulfonates.

[0130] Particularly preferred are dispersing agents from the group of naphthalene sulfonates, such as e.g. Morwet D-425 or Morwet EFW and / or from the group of sodium salts of copolymers of (meth)acrylic acid and styrene, such as e.g. Tersperse 2700 or Atlox Metasperse 500S. d) water-soluble filler

[0131] Suitable water-soluble fillers d) for the purposes of the present invention are fillers selected from the group comprising water-soluble inorganic fillers (dl) and water-soluble organic fillers (d2). Preferably, water- soluble inorganic fillers (dl) are selected from the group of soluble inorganic salts, more preferred potassium sulfate and phosphoric acid salts of the form M3PO4, M2HPO4, or MH2PO4 wherein M is preferably Na, K or NH4. Water-soluble organic fillers (d2) are preferably selected from the group of sugars and urea derivatives, for example lactose, maltodextrin and urea.

[0132] Even more preferred (dl) is selected from the group potassium sulfate or diammonium hydrogen phosphate, and (d2) from lactose and maltodextrin. Most preferably (d2) is lactose. e) water insoluble filler

[0133] Useful inert filler materials e) are all substances typically usable for this purpose in agrochemical compositions. Preference is given to inorganic particles, such as carbonates, silicates and oxides, and also organic substances, such as urea-formaldehyde condensates and celluloses (e.g. Ulmerweiss 6AL, Celite 209, Argirec B21 and B22, Bentone EW, Luz2 talc, Etiquette Violette). Examples include kaolin, rutile, silicon dioxide, finely divided silica, silica gels, and natural and synthetic silicates, and also talc.

[0134] The filler is further preferably selected from the group comprising kaolin, rutile and silicon dioxide. Particular preference is given to kaolin. f) Structure former

[0135] The formulations according to the invention may further comprise a structure former. Suitable for this purpose are particularly polyacrylic acid and salts thereof and especially crosslinked polyacrylates, and also polyurethanes and derivatized polyurethanes and salts thereof. Examples of such suitable acrylates are: (poly)methacrylate, (poly)methylmethacrylate, polyacrylamide, (poly)ethoxyethylmethacrylate, and polymethyl urea resins like Pergopak®M. Pergopak®M is a polymethyl urea resin.

[0136] The structure former is most preferably a polymethyl urea resin. g) Adjuvants and formulation aids

[0137] Useful foam inhibitors are all substances typically usable for this purpose in agrochemical compositions. Preference is given to silicone oil-based defoamers and magnesium stearate.

[0138] Particular preference is given to polydimethylsiloxane absorbed on a solid substrate.

[0139] Possible preservatives are all substances which can customarily be employed in agrochemical agents for this purpose. Suitable examples for preservatives are preparations containing 5-chloro-2-methyl-4- isothiazolin-3-one [CAS-No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [CAS-No. 2682-20-4] or 1.2- benzisothiazol-3(2H)-one [CAS-No. 2634-33-5]. Examples which may be mentioned are Preventol® D7 (Lanxess), Kathon® CG / ICP (Dow), Acticide® SPX (Thor GmbH) and Proxel® GXL (Arch Chemicals). Useful antioxidants are all substances typically usable for this purpose in agrochemical compositions. Preference is given to butylhydroxy toluene.

[0140] Useful dyes are all substances typically usable for this purpose in agrochemical compositions. Examples include titanium dioxide, pigment black, zinc oxide and blue pigments, and also Permanent Red FGR. pH- regulating substances are all substances usually used for this purpose in solid agrochemical agents.

[0141] Citric acid and ascorbic acid are preferred if a pH value is to be adjusted. Particularly preferred is citric acid.

[0142] Moreover, complexing agents can be used for hard water compatibility, like e.g. ethylene diamine tetraacetate.

[0143] Ranges of preference stated in the present invention the different levels of preference should be understood such that they can be combined with one another in permutations, but in any case identical levels of preference and especially the most preferred embodiment / level of preference in each case are to be combined with one another and are indeed disclosed as such a combination.

[0144] Compositions as described in the instant invention that consist solely of the essential components (not optional components) should likewise be considered to be disclosed.

[0145] Percentages - unless stated otherwise - should be regarded as percentages by weight, where the % by weight of the compositions should add up to 100.

[0146] Percentages by weight are always related to the total amount of the composition.

[0147] Unless defined differently, "basic" in the context of the present invention means a pH in aqueous solution with pH > 7.

[0148] The proportion of the active ingredient (component a) in the compositions according to the invention is

[0149] 1.0 - 30 % by weight, further preferred 8-30% by weight, and most preferred 10-20 % by weight.

[0150] The proportion of component (b) in the compositions according to the invention as further active ingredient is

[0151] 0-50 % by weight, further preferred 0-20 % by weight, and most preferred 2-15 % by weight.

[0152] The proportion of the at least one dispersant (component c) in the compositions according to the invention is

[0153] 6-25% by weight, further preferred 8-25% by weight, and most preferred 10-20% by weight.

[0154] The proportion of the water-soluble filler (component d as sum of dl and d2) in the compositions according to the invention is

[0155] 5-60% by weight, further preferred 8-50% by weight, and most preferred 10 - 45 % by weight,

[0156] The proportion of the water insoluble filler (component e) in the compositions according to the invention is

[0157] 5-50% by weight, further preferred 10-48% by weight, and most preferred 15-45% by weight.

[0158] The proportion of the structure former (component f) in the compositions according to the invention is

[0159] 0.5-15% by weight, further preferably 1-10% by weight, and more preferably 3-8% by weight.

[0160] The proportion of the further formulation aids (component g) - if present - in the compositions according to the invention is

[0161] 0-10% by weight, further preferably 0.1-8% by weight, and more preferably 0.1-5% by weight. A preferred embodiment of the invention is compositions comprising components a) 1.0 - 30% by weight b) 0 - 50% by weight c) 6-25% by weight d) 5-60% by weight e) 5-50% by weight f) 0.5-15% by weight g) 0-10% by weight.

[0162] A further-preferred embodiment of the invention is compositions comprising components a) 8-30 % by weight b) 0-20 % by weight c) 8-25% by weight d) 8-50% by weight e) 10-48% by weight f) 1-10% by weight g) 0.1-8% by weight.

[0163] An even further-preferred embodiment of the invention is compositions comprising components a) 10-20% by weight b) 2-15% by weight c) 10-20% by weight d) 10-45% by weight e) 15-45% by weight f) 3-8% by weight g) 0.1-5% by weight.

[0164] In a preferred embodiment a) and b) are present. In one alternative embodiment only a) is present as active ingredient, no b) is present.

[0165] Moreover, the present invention is directed to the use of the polymorphic form A of the compound of formula (1) for controlling animal pests. The term “controlling" means inhibition of animal pest development (including mortality, feeding reduction, and / or mating disruption). It has been surprisingly found that although polymorphic form A has 60% of the water solubility of polymorphic form B, the systemic biological efficacy of polymorphic form A is at the same level as that of polymorphic form B.

[0166] In a particular embodiment, the present invention is directed to controlling animal pests in crops of useful plants including cereals (wheat, rice, triticale, barley, rye, oats), maize, soya bean, potato, sugar beet, sugar cane, tomatoes, pepper, cucumber, melon, carrot, watermelon, onion, lettuce, spinach, leek, beans, Brassica oleracea (e.g. cabbage) and other vegetable species, cotton, tobacco, oilseed rape, and also fruit plants (with the fruits apples, pears, citrus fruits and grapevines). In a particular preferred embodiment the useful plants are fruits and grapes, vegetables and flowers, coffee and cocoa (plantations), potatoes, cotton, cereals, sugar beet, oilseed rape, corn and soybeans. In another particular embodiment of the present invention, the useful plants are transgenic plants.

[0167] The present invention is also directed to a method for controlling animal or microbial pests, wherein the form A of the compound of formula (I) or a plant protection agent as defined above containing the form A of the compound of formula (I), is allowed to act on animal or microbial pests and / or their habitat.

[0168] The control of the animal pests is preferably conducted in agriculture and forestry, and in material protection. Preferably excluded therefrom are methods for the surgical or therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body.

[0169] In another embodiment, the present invention is directed to the use of the form A of the compound of formula (I) for controlling animal pests. The form A of the compound of formula (I) can be advantageously used as a pesticide, in particular in a plant protection agent as described above. Preferably excluded therefrom are uses in methods for the surgical or therapeutic treatment of the human or animal body and in diagnostic methods carried out on the human or animal body.

[0170] In the context of the present application, the term "pesticide" in each case also always comprises the term "plant protection agent".

[0171] All plants and plant parts can be treated in accordance with the invention. Here, plants are to be understood to mean all plants and plant parts such as wanted and unwanted wild plants or crop plants (including naturally occurring crop plants), for example cereals (wheat, rice, triticale, barley, rye, oats), maize, soya bean, potato, sugar beet, sugar cane, tomatoes, pepper, cucumber, melon, carrot, watermelon, onion, lettuce, spinach, leek, beans, Brassica oleracea (e.g. cabbage) and other vegetable species, cotton, tobacco, oilseed rape, and also fruit plants (with the fruits apples, pears, citrus fruits and grapevines). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or cannot be protected by varietal property rights. Plants should be understood to mean all developmental stages, such as seeds, seedlings, young (immature) plants up to mature plants. Plant parts should be understood to mean all parts and organs of the plants above and below ground, such as shoot, leaf, flower and root, examples given being leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds, and also tubers, roots and rhizomes. Parts of plants also include harvested plants or harvested plant parts and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.

[0172] Treatment according to the invention of the plants and plant parts with the form A of the compounds of the formula (I) is carried out directly or by allowing the compounds to act on the surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.

[0173] As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms), and parts thereof are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above. The invention is used with particular preference to treat plants of the respective commercially customary cultivars or those that are in use. Plant cultivars are to be understood as meaning plants having new properties ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.

[0174] The transgenic plants or plant cultivars (those obtained by genetic engineering) which are to be treated with preference in accordance with the invention include all plants which, through the genetic form, received genetic material which imparts particular advantageous useful properties ("traits") to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to levels of water or soil salinity, enhanced flowering performance, easier harvesting, accelerated ripening, higher yields, higher quality and / or a higher nutritional value of the harvested products, better storage life and / or processability of the harvested products. Further and particularly emphasized examples of such properties are increased resistance of the plants against animal and microbial pests, such as against insects, arachnids, nematodes, mites, slugs and snails owing, for example, to toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and Cry IF and also combinations thereof), furthermore increased resistance of the plants against phytopathogenic fungi, bacteria and / or viruses owing, for example, to systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and also resistance genes and correspondingly expressed proteins and toxins, and also increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin (for example the "PAT" gene). The genes which impart the desired traits in question may also be present in combinations with one another in the transgenic plants. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice, triticale, barley, rye, oats), maize, soya beans, potatoes, sugar beet, sugar cane, tomatoes, peas and other types of vegetable, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), with particular emphasis being given to maize, soya beans, wheat, rice, potatoes, cotton, sugar cane, tobacco and oilseed rape. Traits which are particularly emphasized are the increased resistance of the plants to insects, arachnids, nematodes and slugs and snails.

[0175] Crop protection - types of treatment

[0176] The treatment of the plants and plant parts with form A of the compounds of the formula (I) is carried out directly or by action on their surroundings, habitat or storage space using customary treatment methods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, foaming, painting, spreading-on, injecting, watering (drenching), drip irrigating and, in the case of propagation material, in particular in the case of seed, furthermore as a powder for dry seed treatment, a solution for liquid seed treatment, a water-soluble powder for slurry treatment, by incrusting, by coating with one or more coats, etc. It is furthermore possible to apply form A of the compounds of the formula (I) by the ultra-low volume method or to inject the application form of form A of the compound of the formula (I), or the form A of the compound of the formula (I) itself, into the soil.

[0177] A preferred direct treatment of the plants is foliar application, i.e. form A of the compounds of the formula (I) is applied to the foliage, where treatment frequency and the application rate should be adjusted according to the level of infestation with the pest in question.

[0178] In the case of systemically active compounds, form A of the compounds of the formula (I) also accesses the plants via the root system. The plants are then treated by the action of form A of the compounds of the formula (I) on the habitat of the plant. This may be done, for example, by drenching, or by mixing into the soil or the nutrient solution, i.e. the locus of the plant (e.g. soil or hydroponic systems) is impregnated with a liquid form of form A of the compounds of the formula (I), or by soil application, i.e. form A of the compounds of the formula (I) according to the invention is introduced in solid form (e.g. in the form of granules) into the locus of the plants, or by drip application (often also referred to as "chemigation"), i.e. the liquid application of form A of the compounds of the formula (I) according to the invention from surface or sub-surface driplines over a certain period of time together with varying amounts of water at defined locations in the vicinity of the plants. In the case of paddy rice crops, this can also be done by metering form A of the compounds of the formula (I) in a solid application form (for example as granules) into a flooded paddy field.

[0179] Table 8: Materials used in the examples

[0180] Kaolin W: Aluminum hydrosilicate, Erbsloh Lohrheim GmbH & Co. KG, Lohrheim, Germany.

[0181] Kaolin Tec: Aluminum hydrosilicate; Ziegler & Co. GmbH, Wunsiedel, Germany.

[0182] Tersperse ® 2700: naphthalene sulfonate formaldehyde-condensate, sodium salt, Indorama Ventures, The Woodlands, Texas, USA.

[0183] Rhodorsil ® Antimousse EP 6703: absorbed polydimethylsiloxane, Solvay.

[0184] Morwet ® EEW: alkyl naphthalene sulfonate, sodium salt, Nouryon, Sternungsund, Sweden.

[0185] Morwet ® D-425: naphthalene sulfonate, sodium salt, Nouryon, Sternungsund, Sweden.

[0186] Pergopak ® M: Polymethyl urea resin; Huber Martinswerk, Bergheim, Germany.

[0187] Atlox Metasperse™ 550S: modified styrene acrylic polymer, Croda, Great Britain.

[0188] Trilon ® B Powder: Tetrasodium ethylene diamine tetraacetate, BASE, Ludwigshafen, Germany.

[0189] Flupyradifurone, Spiromesifen, Spidoxamat: BayerAG.

[0190] All polymorphs of form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one used have at least a content of form A of 85 % (vs. form B).

[0191] Tests and Methods used in the examples

[0192] Methods

[0193] All data which is part of the present application has been prepared according to the methods described below unless otherwise indicated. The samples used for measurement were directly used and did not undergo any further sample preparation. XRPD

[0194] X-Ray diffraction patterns were recorded at room temperature using XRD -diffractometers X'Pert PRO (PANalytical) and STOE STADI-P (radiation Cu K alpha 1, wavelength 1.5406 A). All X-Ray reflections are quoted as °26 (theta) values (peak maxima) with a resolution of + 0.2°. Raman

[0195] Raman spectra were recorded at room temperature using FT-Raman-spectrophotometers (model RFS 100 and MultiRam) from Bruker. Resolution was 2 cm1. Measurements were performed in glass vials or aluminium discs.

[0196] IR IR-ATR-spectra were recorded at room temperature using a FT-IR-spectrophotometer Tensor 37 with universal diamond ATR device or a Eumos with ATR device from Bruker. Resolution was 2 cm1.

[0197] DSC

[0198] DSC thermograms were recorded using DSC calorimeters DSC 3 and DSC 3+ from Mettler or Diamond DSC and DSC 8000 from Perkin Elmer. The measurements were performed with a heating rate of 20 Kmin ’or 2 Kmin1using perforated aluminium pans. Flow gas was nitrogen.

[0199] Examples

[0200] I Polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

[0201] LI Preparation of polymorphic form A

[0202] Example 1

[0203] 430 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011 / 051151, are dissolved in 60 ml of toluene and the solution is filtered. One fourth of the solution is stored at room temperature and ambient humidity until the solvent is evaporated. The residue is tested by thermal analysis and corresponds to the title compound in the polymorphic form A.

[0204] Example 2

[0205] 404 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011 / 051151, are dissolved in 60 ml of methanol and the solution is filtered. One fourth of the solution is stored in a refrigerator until the solvent is evaporated. The residue is tested by thermal analysis and corresponds to the title compound in the polymorphic form A.

[0206] Example 3

[0207] 405 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011 / 051151, are dissolved in 20 ml of ethyl acetate and the solution is filtered. 5 ml of n-heptane are added to a quarter of the solution and this is stored at room temperature and ambient humidity until the solvent is evaporated. The residue is tested by X-ray diffraction and corresponds to the title compound in the polymorphic form A.

[0208] Example 4

[0209] 413 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011 / 051151, are dissolved in 60 ml of isopropanol and the solution is filtered. One fourth of the solution is stored at room temperature and ambient humidity until the solvent is evaporated. The residue is viscous. It is scratched and left to stand at room temperature and ambient conditions until it has crystallized. The residue is tested by X-ray diffraction and corresponds to the title compound in the polymorphic form A.

[0210] Example 5

[0211] 106 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011 / 051151 are suspended in 1 ml of water and shaken in an Eppendorf Thermomix at 25 °C (1400 rpm, 30 min shaking / 30 min stop). After one week the suspension is dried at room temperature and ambient humidity. The residue is tested by IR spectroscopy and corresponds to the title compound in the polymorphic form A.

[0212] II. Polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan- 2(5H)-one

[0213] II.l Preparation of polymorphic form B

[0214] 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B has been produced as described in Preparation Example 3 of WO-A-2011 / 051151.

[0215] III. Water solubility of Flupyradifurone polymorphs

[0216] The water solubility of FPF polymorph A and B was determined by saturating a certain amount of demineralized water with the respective polymorph, stirring the resulting saturated suspension overnight, filtering the undissolved solid residue, and measuring the dissolved concentration of FPF in the filtrate.

[0217] Table 9: Measured water solubility of FPF Polymorphs

[0218] IV Flupyradifurone WG Formulation Examples

[0219] IV.1 Preparation of Flupyradifurone WG Formulations

[0220] A mixture of Flupyradifurone, and optionally a second active ingredient, and other formulation ingredients (see examples) were, as known in the art, mixed and ground in a 4" air jet mill Hosokawa 100 AS (injector air 5.5 bar, grinding air 4.5 bar, throughput 100 g / min), moistened with water and extruded on a Fuji Paudal Dome extruder (die size 1 mm) to a WG and post-dried in a fluidized bed dryer until a product temperature of approx. 45 °C is reached. Table 10: Composition of WG formulations with both polymorphs

[0221] Table Ila & b: Storage stability data

[0222] No significant difference in storage stability data could be observed using the two different polymorphic forms of Flupyradifurone.

[0223] Table 12: Further compositions of WG formulations prepared with polymorph A

[0224] Table 13 a, b, c: Stability data of selected examples from table 12

[0225] No significant difference in storage stability data could be observed using the two different polymorphic forms of Flupyradifurone. The formulations with both polymorph types are well within the tolerances.

[0226] Determination of wetting time (according to CIPAC MT 53.3):

[0227] A 250 ml glass beaker is filled with water (CIPAC D). Approximately 5 g of product is dropped onto the surface of the water. The time taken for complete wetting is determined.

[0228] Determination of the pH value (according to the CIPAC MT 75.3): The pH value is measured with a common pH glass electrode in a 1% dispersion of the granules in demineralized water at 23 °C.

[0229] Determination of suspensibility (according to CIPAC MT 184.1): A 1% suspension is dispersed in water (CIPAC C) in a 250 mL graduated cylinder. The mixture is equilibrated for 30 minutes. Subsequently, the upper 9 / 10 of the suspension is removed. The remaining 1 / 10 are dried up and the residue (sediment) is determined gravimetrically. Suspensibility is defined as:

[0230] 10 / 9 * 100 * (sample quantity [g]*proportion a.i. [%] / 100 - residue [g]) / (sample quantity [g ^-proportion a.i. [%] / 100)

[0231] Thus, a value of 100 % corresponds to an even distribution of all insoluble components over the sample volume.

[0232] Determination of the wet sieve residue (according to CIPAC MT 185):

[0233] 25 g of granules are placed in a beaker in 250 mL of water. After one minute, stirring is carried out with a magnetic stirrer for 5 minutes. Subsequently, the dispersion and the washing water for cleaning the beaker are transferred to the corresponding sieve. The sieve is then rinsed with cold water until no change in the residue on the sieve is visible (max. 10 min). After the sieve has drained, the residue is quantitatively transferred to an exhaust steam tray with demineralized water, allowed to dry and the residue is determined gravimetrically.

[0234] V Biological Testing of Flupyradifurone + Spiromesifen WG 24, Comparison Polymorph A and B

[0235] The formulations according to the invention were tested in the greenhouse on Myzus persicae (MYZUPE) on pepper and Aphis gossypii (APHIGO) on cotton; with mixed populations, pre-infested, contact application.

[0236] The application rate was 100 and 300 1 / ha respectively, with track sprayer, contact and translaminar. Five repetitions were performed at a time. The tests with MYZUPE were carried out at 20 °C and with APHIGO at 23 °C. The evaluation was carried out after 1, 4 and 7 days (1, 4, 7 d) after application.

[0237]

[0238] Although polymorphic form A of Flupyradifurone shows a significant lower water solubility, no significant differences in biological efficacy could be observed independent of application rate and water volumes used.

Claims

Claims:

1. A solid agrochemical formulation comprising a) the crystalline form A of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one of formula (1)which in a X-ray powder diffractogram at 25 °C and Cu-Ka 1 radiation displays at least 3 of the following characteristic reflections, quoted as 20 value + 0.2°: 21,0; 22,4 and 29,4, wherein at least 85 % by weight of 4-[(6-chloro-3-pyridylmethyl)(2,2- difhioroethyl)amino]furan-2(5H)-one of formula (1) is present in its crystalline form A, c) at least one dispersant, d) at least one water soluble filler, e) at least one water insoluble filler and f) at least one structure former, wherein a) is present in 1.0 - 30 % by weight, c) is present in 6-25% by weight, d) is present in 5-60% by weight, e) is present in 5-50% by weight and f) is present in 0.5-15% by weight.

2. An agrochemical formulation according to claim 1, wherein at least 95 % by weight of 4-[(6- chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of formula (1) is present in its crystalline form A.

3. An agrochemical formulation according to claim 1 or 2, comprising components in a) 1.0 - 30% by weight c) 6-25% by weight d) 5-60% by weight e) 5-50% by weight f) 0.5-15% by weight.

4. An agrochemical formulation according to claim 1 to 3, wherein components b) at least one other active ingredient and / or g) other common adjuvants or formulations aids are present.

5. An agrochemical formulation according to claim 4, comprising a) the polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan- 2(5H)-one, b) at least one other active ingredient c) at least one dispersant d) at least one water soluble filler e) at least one water insoluble filler f) at least one structure former and g) other common adjuvants or formulations aids.

6. An agrochemical formulation according to claim 4 or 5 comprising the components in a) 10-20% by weight b) 2-15% by weight c) 10-20% by weight d) 10-45% by weight e) 15-45% by weightf) 3-8% by weight g) 0.1-5% by weight.

7. An agrochemical formulation according to claims 4 to 6, wherein the other active ingredient is selected from the group consisting of spiromesifen and spidoxamat.

8. An agrochemical formulation according to any of the preceding claims, characterized in that c) is selected from the group of the sodium salts of alkylated naphthalene sulfonates and the sodium salts of dioctylsulfosuccinic acid.

9. An agrochemical formulation according to any of the preceding claims, characterized in that d) is selected from the group comprising water-soluble inorganic fillers (dl) and water-soluble organic fillers (d2).

10. An agrochemical formulation according to any of the preceding claims, characterized in that (dl) is selected from the group of potassium sulfate and phosphoric acid salts of the form M3PO4, M2HPO4, or MH2PO4 wherein M is preferably Na, K or NH4; and the water-soluble organic fillers (d2) are preferably selected from the group of sugars and urea derivatives.

11. An agrochemical formulation according to any of the preceding claims, characterized in that the water insoluble filler (e) is selected from the group comprising kaolin, rutile and silicon dioxide.

12. An agrochemical formulation according to any of the preceding claims, characterized in that (f) is selected from the group of crosslinked poly acrylates, polyurethanes and derivatized polyurethanes and salts thereof.

13. Use of the polymorphic form [A] according to any of the preceding claims for the production of an agrochemical solid formulation with improved storage stability.