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

Abstract

The present invention relates to agrochemical formulations comprising a crystalline form A of 4-[(6-chloro-3-pyridylmethyl) (2, 2-difluoroethyl) amino] furan-2 (5H)-one of formula (1) and their use in plant protection applications. # imgabs0 #

Description

SUMMARY OF THE INVENTION

[0002] The present invention relates to a novel agrochemical formulation comprising a novel crystalline form of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of formula (1)

[0003]

[0004] It is polymorphic form A, and also relates to a process for its preparation and the novel crystalline form itself, as well as its use for the preparation of agrochemical formulations and in plant protection applications, in particular its use as an insecticide.

[0005] The compound of formula (1) with the common name flupyradifurone and the IUPAC name 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one and its preparation method are known from WO-A-2007 / 115644. Its preparation method is also known from WO-A-2009 / 036899.

[0006] Amorphous and crystalline forms of the compound of formula (1) are known from WO-A-2011 / 051151. The crystalline form disclosed in WO-A-2011 / 051151 is marked therein as being thermodynamically stable and is characterized in that it is irradiated at 25°C using Cu-Kα radiation. The X-ray powder diffraction pattern has at least 3 of the following 2θ (2θ) values ​​as characteristic signals:

[0007] 2θ=16.8°±0.2 2θ=17.8°±0.2 2θ=20.2°±0.2 2θ=21.7°±0.2 2θ=23.6°±0.2 2θ=23.9°±0.2 2θ=24.7°±0.2 2θ=25.3°±0.2

[0008] The crystalline form disclosed in WO-A-2011 / 051151 is polymorph Form B. Background Art

[0009] Polymorphism is the ability of a compound to crystallize in different crystalline phases with different molecular arrangements and / or conformations in the crystal lattice. Therefore, polymorphs are different crystalline forms of the same pure compound. Due to different molecular arrangements and / or conformations, polymorphs exhibit different physical, chemical and biological properties. The properties that may be affected include, but are not limited to, solubility, dissolution rate, stability, optical properties and mechanical properties. The relative stability of polymorphs depends on their free energy, i.e., more stable polymorphs have lower free energy. Under a set of prescribed experimental conditions, only one polymorph has the lowest free energy. The polymorph is a thermodynamically stable form, and all other one or more polymorphs are called metastable forms. The metastable form is a thermodynamically unstable form, but due to its relatively slow transformation rate, it can still be prepared, separated and analyzed.

[0010] The occurrence of active substances in different polymorphic forms (hereinafter also referred to as polymorphs or crystalline forms) is of decisive importance for the industrial-scale preparation and development of formulations containing the active substances, since unwanted phase changes can lead to thickening and potential solidification of the formulation and / or large crystals, which can lead to clogging of application equipment (e.g. nozzles in agricultural application machinery). Therefore, knowledge of the existence of crystalline modifications and their properties is of great practical significance. Each polymorph is characterized by a specific, uniform packing and arrangement of the molecules in the solid state. However, it is generally impossible to predict whether a given compound forms polymorphs and, if so, which physical and biological properties the different polymorphs may have.

[0011] In addition, pseudopolymorphic forms may occur, known as hydrates or solvates. Solvates are crystalline molecular compounds in which molecules of the crystallization solvent are incorporated into a host lattice consisting of unsolvated molecules. Hydrates are a special case of solvates, in which the incorporated solvent is water. The presence of solvent molecules in the lattice influences the interactions between the molecules and gives each solvate unique physical properties. Therefore, solvates have their own characteristic values ​​for internal energy, enthalpy, entropy, Gibbs free energy and thermodynamic activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1a: X-ray powder diffraction pattern of polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

[0013] Figure 1b: FT Raman spectrum of polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

[0014] Figure 1c: IR spectrum of polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

[0015] Figure 1d: DSC thermal analysis of polymorph Form A picture

[0016] Figure 2a: X-ray powder diffraction pattern of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

[0017] Figure 2b: FT Raman spectrum of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

[0018] Figure 2c: IR spectrum of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

[0019] Figure 2d: DSC thermal analysis of polymorph Form B picture DETAILED DESCRIPTION

[0020] As mentioned 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 of formula (1),

[0021]

[0022] It is also referred to hereinafter as fluopyrrolone (FPF).

[0023] 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 a thermodynamically stable form and has improved properties compared to the polymorphic form B disclosed in WO-A-2011 / 051151 (which, although kinetically quite stable, was found only in a metastable state).

[0024] In particular, it has now surprisingly been found that polymorphic form A has improved storage stability at elevated temperatures.

[0025] Furthermore, the water solubility of Form A is significantly lower than that of Form B. However, despite the lower solubility, it was surprisingly found that its biological activity / efficacy (especially in the formulations of the present invention) is not reduced.

[0026] The compound 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one contains hydrogen atoms at different positions, and the hydrogen atoms can be any hydrogen isotope, i.e.1 H or 2 H (deuterium). Therefore, 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).

[0027] 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 diffraction based on the corresponding diffraction pattern, which was recorded at 25° C. using Cu-Kα1 radiation. The polymorphic form A according to the invention exhibits at least 3, generally at least 5, in particular at least 7, more in particular at least 10 and especially all reflections which are reported as numerical values ​​below:

[0028] Table 1: X-ray reflections of polymorph Form A

[0029]

[0030]

[0031] The polymorphic form A of the present invention is further characterized by the X-ray powder diffraction pattern shown in Figure [1a].

[0032] In a preferred embodiment, the polymorphic form A of the present invention exhibits at least 3, in particular at least 5, more in particular at least 7, even more in particular at least 10 and especially all of the following characteristic reflections recorded in 2θ values ​​±0.2°: 15.0, 20.1, 21.0, 22.4, 29.4, 33.1 and 33.2.

[0033] In one embodiment, polymorph Form A of the present invention exhibits at least the following characteristic reflections recorded in 2-theta values: 21.0, 22.4 and 29.4.

[0034] In one embodiment, polymorph Form A of the present invention exhibits at least the following characteristic reflections recorded in 2θ values: 15.0, 20.1, 21.0, 22.4 and 29.4.

[0035] In one embodiment, polymorph Form A of the present invention exhibits at least the following characteristic reflections recorded in 2-theta values: 15.0, 20.1, 21.0, 22.4, 29.4, 33.1 and 33.2.

[0036] The polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by Raman spectroscopy based on the corresponding spectra recorded at 25°C with a laser wavelength of 1064 nm and a resolution of 2 cm -1 The polymorphic form A of the invention exhibits at least 3, generally at least 5, in particular at least 7 and especially all bands reported below as peak maxima:

[0037] Table 2: Raman bands of Form A

[0038]

[0039]

[0040] The polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by infrared spectroscopy based on the corresponding spectra recorded at 25°C using a universal diamond ATR apparatus with a resolution of 2 cm -1 The polymorphic form A of the invention exhibits at least 3, generally at least 5, in particular at least 7 and especially all bands reported below as peak maxima:

[0041] Table 3: IR bands of Form A

[0042]

[0043]

[0044] In addition to polymorphic form A, polymorphic form B is known from WO-A-2011 / 051151 and is further characterized below.

[0045] 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 diffraction based on the corresponding diffraction pattern, which was recorded at 25° C. using Cu-Kα1 radiation. Polymorphic form B exhibits at least 3, generally at least 5, in particular at least 7, more in particular at least 10 and especially all reflections reported below as numerical values:

[0046] Table 4: X-ray reflections of polymorph Form B

[0047]

[0048]

[0049] Polymorph Form B is further characterized by the X-ray powder diffraction pattern shown in Figure [2a].

[0050] The polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by Raman spectroscopy based on the corresponding spectra recorded at 25° C. with a laser wavelength of 1064 nm and a resolution of 2 cm -1 The polymorphic form B of the invention exhibits at least 3, typically at least 5, in particular at least 7 and especially all bands reported below as peak maxima:

[0051] Table 5: Raman bands of Form B

[0052]

[0053]

[0054] The polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by infrared spectroscopy based on the corresponding spectra recorded at 25°C using a universal diamond ATR apparatus with a resolution of 2 cm -1 The polymorphic form B of the invention exhibits at least 3, typically at least 5, in particular at least 7 and especially all bands reported below as peak maxima:

[0055] Table 6: IR bands of Form B

[0056]

[0057]

[0058] Embodiment of preparing crystal form A

[0059] In another embodiment, the present invention is directed to a method for preparing polymorph Form A, comprising the steps of:

[0060] a) diluting and / or suspending the compound of formula (1) in a suitable solvent or solvent mixture;

[0061] b) adjusting the temperature to 0 to 25° C., optionally by heating or cooling; and

[0062] c) storing the solution or slurry obtained in step b) at a temperature of 0 to 25°C until the solvent evaporates and crystals of polymorphic Form A are formed.

[0063] The chemical preparation of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of formula (1) is known from the prior art, such as WO-A-2007 / 115644 or WO-A-2009 / 036899. Thus, the compound of formula (1) used in step a) can be prepared according to WO-A-2007 / 115644 or WO-A-2009 / 036899, to which the present invention is hereby fully incorporated.

[0064] Preferably, the chemical preparation of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one is carried out according to WO-A-2007 / 115644 with butyronitrile as solvent. The crystallization and filtration of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one are preferably carried out in butanol. After filtration, the crystals obtained are preferably washed with ethanol.

[0065] The compound of formula (1) in step a) can be essentially 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 an amorphous form, or in a mixture of different polymorphic forms, or in a mixture containing an amorphous form and one or more different polymorphic forms.

[0066] 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 solvents, such as aromatic solvents or alcohols or esters or water, preferably toluene, methanol, ethanol, butanol, ethyl acetate, isopropanol or water.

[0067] The solution of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can also be prepared by transferring the reaction mixture containing 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one obtained by the chemical reaction into the solvent or solvent mixture of the present invention after removing reagents and / or by-products as necessary.

[0068] In step b), the temperature of the solution or slurry is adjusted to a temperature of 0° C. to 25° C. This can be achieved by cooling or heating, or by waiting until the temperature adjusts to room temperature (if the temperature is 0° C. to 25° C.).

[0069] In step c), the solution or slurry obtained in step b) is stored at a temperature of 0°C to 25°C until the solvent evaporates and crystals of polymorphic Form A are formed. Preferably, polymorphic Form A is separated from the solvent or solvent mixture by allowing the solution or slurry to stand under the crystallization conditions of step c) until at least 90% by weight of the solvent or solvent mixture evaporates.

[0070] Crystallization of polymorphic Form A may be promoted or accelerated by seeding with Form A crystals.

[0071] Isolation of polymorphic form A from the mother liquor is carried out by conventional techniques known in the art, for example by filtration, centrifugation or by decantation.

[0072] The isolated polymorphic form A can be optionally washed with any solvent, preferably with the solvent or solvent mixture used for crystallization, with water or with a mixture of a solvent or solvent mixture and water. The washing step can be optionally repeated, wherein washing with water is usually the last washing step. Washing is usually carried out at a temperature below 30° C., usually below 25° C. and in particular below 20° C., optionally at 0° C. In another optional step, the crystals of polymorphic form A can be dried before being used for further processing.

[0073] By the crystallization according to the invention, at least 85%, in particular 90% and most preferably at least ≥95% of crystalline form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be obtained.

[0074] This means that, apart from other possible impurities, the amount of form B or amorphous form remaining is preferably <15%, in particular <10% and most preferably <5%.

[0075] The content of the crystalline form A of the present invention is analyzed by IR spectroscopy. Based on the calculated electronic mixed IR spectrum (mixed in 5% steps by a software calculator), a calibration curve is generated using PLS regression. The proportion of different crystalline forms is calculated by this curve. Due to the calibration accuracy, the above wording does not exclude a 100% content of polymorphic form A.

[0076] Therefore, a particular embodiment of the present invention relates to 4-[(6-chloro-3-pyridinylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, which consists of at least 85% and typically at least 90% or at least ≥95% of polymorphic form A.

[0077] Another alternative embodiment of the present invention is a method for preparing an aqueous dispersion of fluoropyrafurone, wherein the crystalline form of fluoropyrafurone can be steered / controlled according to grinding parameter changes. Depending on the grinding parameters, the relative amount of crystalline form A in a mixture of crystalline form B and crystalline form A of fluoropyrafurone can be maintained or increased (see Table 11).

[0078] It is known that the choice of grinding media during the grinding process affects the energy input during the grinding process (Austin, LG, Klimpel, RR and Luckie, PT, 1984. Process engineering of size reduction: ball milling. Society of Mining Engineers of the AIME), so denser grinding media (such as zirconium oxide beads) will induce higher energy, which produces effects such as increased outlet temperature of the grinding base and potential reduction in viscosity of the grinding base, thereby causing a direct increase in grinding efficiency. We observed that under these conditions, the relative amount of Form A of Fluoropyrrolidone can be increased from a lower amount to Form A becoming the main component in the mixture.

[0079] In contrast, the use of less dense grinding media materials (e.g., glass beads) does not affect the temperature of the grinding process, and thus Form A does not increase during grinding using glass beads at room temperature within the limits of analytical detection.

[0080] Embodiment of agricultural chemical formulation containing crystalline form A

[0081] In another embodiment, the present invention relates to a plant protection agent in the form of a conventional formulation (agrochemical formulation) containing 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 (I) 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), for example the amorphous form or the crystalline form (form B) disclosed in WO-A-2011 / 051151.

[0082] For the avoidance of doubt, the term "at least 85 wt%" or "at least 90 wt%" or "at least 95 wt%" means "85-100 wt%" or "90-100 wt%" or "95-100 wt%".

[0083] Formulation type

[0084] Conventional formulations (agrochemical formulations) are, for example, water-soluble liquids (SL), 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 other possible formulation types are described, for example, by Crop Life International in the following documents: Pesticide Specifications, Manual on development and use of FAO and WHO specifications for pesticides, FAO Plant Production and Protection Papers-173 (prepared by the Joint Food and Agriculture Organization / World Health Organization (FAO / WHO) Meeting on Pesticide Specifications, 2004, ISBN: 9251048576).

[0085] Preferred formulations or use forms contain auxiliary agents, such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, antifreeze agents, biocides, thickeners and / or other auxiliary agents, such as adjuvants. An adjuvant in the context of the present invention is a component that enhances the biological effect of a formulation, without the component itself having any biological effect. Examples of adjuvants are agents that promote retention, spreading, attachment to or penetration of leaf surfaces.

[0086] The composition of the present invention can be provided to the end user as a ready-to-use formulation, i.e., the composition can be applied directly to plants or seeds by a suitable device (e.g., a spray or dusting device). Alternatively, the composition can be provided to the end user in the form of a concentrate, which must be diluted before use, preferably with water.

[0087] These preparations are prepared in a known manner, for example by mixing a compound of formula (I) with an auxiliary agent, such as an extender, a solvent and / or a solid carrier and / or other auxiliary agents, such as a surfactant. The preparation can be prepared in a suitable device, or before or during application.

[0088] The composition of the present invention may be any conventional Composition type, such as solutions (e.g., aqueous solutions), emulsions, water-based and oil-based suspensions, powders (e.g., wettable powders, soluble powders), dusts, pastes, granules (e.g., soluble granules, granules for broadcasting), suspension concentrates, natural or synthetic products impregnated with the compound combination of the present invention, fertilizers, and microcapsules in polymeric substances. The compound combination of the present invention may be in a suspended, emulsified, or dissolved form. Examples of particularly suitable composition types are solutions, water-soluble concentrates (e.g. SL, LS), dispersible concentrates (DC), suspensions and suspension concentrates (e.g. SC, OD, OF, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME, SE), capsules (e.g. CS, ZC, ZS, ZW), pastes or gels (e.g. PA, GD), wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressed preparations (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticide preparations (e.g. LN) and gel preparations for treating plant propagation materials such as seeds (e.g. GW, GF). These and other composition types are defined by the Food and Agriculture Organization of the United Nations (FAO). An overview is given in "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 7th edition, March 2017, Croplife International.

[0089] Particular preference is given to formulations in the form of suspensions and suspension concentrates (eg SC, OD, OF, FS).

[0090] These preparations are prepared in a known manner, for example by mixing the crystalline form A (polymorph form A) of the compound of formula (I) with conventional additives, such as conventional extenders and solvents or diluents, colorants, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and water.

[0091] Preparations of the present invention

[0092] An exemplary description of the formulation of the present invention is as follows:

[0093] In a preferred embodiment, the agricultural chemical formulation comprises

[0094] a) polymorphic form A of 4-[(6-chloro-3-pyridinylmethyl)(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.

[0095] The remaining less than 15 wt. % (preferably less than 10 wt. %, more preferably less than 5 wt. %) contains other polymorphic forms of the compound of formula (I), such as the amorphous form or the crystalline form disclosed in WO-A-2011 / 051151.

[0096] For the avoidance of doubt, the term "at least 85 wt%" or "at least 90 wt%" or "at least 95 wt%" means "85-100 wt%" or "90-100 wt%" or "95-100 wt%".

[0097] This definition applies to all references to polymorphic form A, unless expressly stated otherwise in the present invention.

[0098] In another preferred embodiment, the formulation comprises

[0099] a) polymorphic form A of 4-[(6-chloro-3-pyridinylmethyl)(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.

[0100] b) one or more dispersants,

[0101] c) one or more rheology control agents (rheology modifiers),

[0102] d) optionally one or more pH buffers,

[0103] e) optionally one or more defoaming agents,

[0104] f) optionally one or more biocides,

[0105] g) optionally one or more antifreeze agents, and

[0106] h) Make up to 1 L (liter) of carrier (filler).

[0107] In another preferred embodiment, the formulation comprises

[0108] a) polymorphic form A of 4-[(6-chloro-3-pyridinylmethyl)(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.

[0109] b) one or more dispersants,

[0110] c) one or more rheology control agents (rheology modifiers),

[0111] d) one or more pH buffers,

[0112] e) one or more defoaming agents,

[0113] f) one or more biocides,

[0114] g) one or more antifreeze agents, and

[0115] h) Make up to 1 L (liter) of carrier (filler).

[0116] In a preferred embodiment, the polymorphic form A a) of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one as defined above is contained in the composition of the present invention in a concentration range of 200-600 g / L, preferably in a concentration range of 300-500 g / L and most preferably in a concentration range of 400-500 g / L.

[0117] In another preferred embodiment of the present invention, the dispersant b) is present in a concentration range of 10-200 g / L, preferably in a concentration range of 20-150 g / L, more preferably in a concentration range of 40-100 g / L, even more preferably in a concentration range of 50-90 g / L and most preferably in a concentration range of 60-80 g / L.

[0118] In yet another embodiment of the present invention, the rheology control agent c) is present in a concentration range of 0.1-10 g / L and preferably 6-10 g / L.

[0119] In one embodiment of the present invention, the pH buffer d) is present in a concentration range of 0-1 g / L, preferably the pH buffer is necessary and is present in 0.01-10 g / L.

[0120] In one embodiment of the present invention, the antifoaming agent e) is present in a concentration range of 0.1-2 g / L.

[0121] In one embodiment of the present invention, the biocide f) is present in a concentration range of 0.1-3 g / L.

[0122] In one embodiment of the present invention, the antifreeze agent g) is present in a concentration range of 5-100 g / L, preferably 10-100 g / L.

[0123] Preferably, the volume is made up to 1 L with the carrier (filler) according to the invention, wherein even more preferably the carrier is water.

[0124] In a preferred embodiment, the formulation comprises

[0125] a) The concentration range is 400-500g / L,

[0126] b) The concentration range is 60-80g / L,

[0127] c) concentration range of 6-10 g / L, and

[0128] h) Make up to 1L of water.

[0129] In a preferred embodiment, the formulation comprises

[0130] a) The concentration range is 400-500g / L,

[0131] b) The concentration range is 60-80g / L,

[0132] c) The concentration range is 6-10g / L,

[0133] d) The concentration range is 0.01-10g / L,

[0134] e) The concentration range is 0.1-2g / L,

[0135] f) The concentration range is 0.1-3g / L,

[0136] g) concentration range is 10-100 g / L, and

[0137] h) Make up to 1L (liter) of water.

[0138] Other adjuvants and auxiliary agents not listed here may be present in component i), such as adhesives, stickers and colorants, antioxidants, light stabilizers (especially UV stabilizers), other agents to improve the chemical and / or physical stability and butylated hydroxytoluene [3.5-di-tert-butyl-4-hydroxytoluene, CAS No. 128-37-0].

[0139] If the formulation is used as a seed coating formulation, component i) is essential.

[0140] When treating seed, care must generally be taken to select the amount of crystalline form A of the compound of formula (I) and / or the amount of other additives applied to the seed so that germination of the seed is not adversely affected or the plant grown therefrom is not damaged. This must be ensured in particular for active compounds which can exhibit phytotoxic effects at certain application rates.

[0141] Typically, the crystalline form A of the compound of formula (I) is applied to the seeds in a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art.

[0142] The crystalline form A of the compound of formula (I) can be converted into conventional seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seeds, as well as ULV formulations.

[0143] The crop protection formulations may also comprise one or more further active substances (k) selected from the group consisting of herbicides, insecticides, acaricides, fungicides, safeners and / or plant growth regulators.

[0144] Furthermore, within the preferred range described herein, different preference levels should be understood such that they can be combined with one another in permutations and combinations, but in any case the same preference levels and in particular the most preferred embodiments / preferred levels in each case will be combined with one another and are indeed disclosed in such combinations.

[0145] The above compositions consisting only of the essential components (no optional components) should also be considered as disclosed.

[0146] The adjuvants used may be substances which are suitable for imparting particular properties (e.g. certain physical, technical and / or biological properties) to the formulations of the compounds of formula (I) or to the use forms prepared from these formulations (e.g. ready-to-use pesticides, such as spray liquors or seed dressing products).

[0147] Dispersant b)

[0148] As used herein, the term "dispersant" refers to a substance known in the art for stabilizing solid colloids of active ingredients. Dispersants The surfactant may be an ionic (cationic or anionic), amphoteric or nonionic surfactant, for example an ionic or nonionic or amphoteric dispersant, emulsifier, foam former, dispersant, wetting agent and any mixture thereof, including standard surface-active substances present in the formulation of active agrochemical ingredients.

[0149] Examples of suitable anionic surfactants include, but are not limited to

[0150] -Salts of polyacrylic acid

[0151] -Salts of polymers of acrylic acid / acrylate mixtures

[0152] -Salts of polymers of acrylic acid / styrene mixtures

[0153] -

[0154] -Salts of lignin sulfonic acid (e.g. sodium lignin sulfonate)

[0155] -Salts of phenolsulfonic acid

[0156] -Salts of condensation products of phenolsulfonic acid and formaldehyde

[0157] - salts of naphthalenesulfonic acid,

[0158] -Salt of condensation product of naphthalenesulfonic acid and formaldehyde

[0159] -Salts of condensed naphthalene or alkylnaphthalene sulfonates

[0160] -Salts of sulfonates of dodecylbenzene and tridecylbenzene

[0161] -

[0162] -Salts of sulfosuccinate or sulfosuccinamate

[0163] -Alkyl sulfate salts

[0164] -Salts of alkyl polyethoxylated and / or polypropoxylated sulfates

[0165] -Salts of paraffin sulfonates

[0166] -Salts of alkyl sulfonates

[0167] -Salts of alkyl polyethoxylated and / or polypropoxylated sulfonates

[0168] -Salts of aryl sulfate

[0169] -Salts of aryl polyethoxylated and / or polypropoxylated sulfates

[0170] -Salts of aryl sulfonates

[0171] -Salts of aromatic polyethoxylated and / or polypropoxylated sulfonates

[0172] -Salts of alkyl aryl sulfates

[0173] -Salts of alkylaryl polyethoxylated and / or polypropoxylated sulfates

[0174] -Salts of alkylaryl sulfonates

[0175] -Salts of alkylaryl polyethoxylated and / or polypropoxylated sulfonates

[0176] -

[0177] -Salts of diphenyl sulfonate and diphenyl ether sulfonate

[0178] -Salts of α-olefin sulfonates

[0179] -Salts of sulfonic acid esters of fatty acids and oils

[0180] -α-sulfonated methyl ester salt

[0181] - Salts of taurine derivatives (preferably taurine alkyl esters)

[0182] -Isethionate salts

[0183] -Alkyl phosphate salts

[0184] -Salts of aryl phosphates

[0185] -Salts of alkyl aryl phosphates

[0186] - Salts of phosphoric acid esters of polyethoxylated and / or polypropoxylated aliphatic linear or branched alcohols

[0187] - Salts of phosphoric acid esters of polyethoxylated and / or polypropoxylated aromatic alcohols

[0188] -Protein hydrolysate

[0189] - Lignin sulfite wastewater

[0190] -Salt of polystyrene sulfonic acid

[0191] -Polyvinylsulfonic acid salt

[0192] -Carboxylic acid ester salt

[0193] - Salts of ether carboxylates

[0194] Any reference to salts in this paragraph preferably refers to the corresponding alkali metal salts, alkaline earth metal salts and ammonium salts. Examples of suitable cationic surfactants include, but are not limited to

[0195] Compounds containing units comprising primary, secondary, tertiary and / or quaternary amino groups, which units may form part of the main polymer chain or may be carried by pendant substituents directly attached thereto.

[0196] - cationic polymers based on acrylamide and methacrylamide,

[0197] -N-vinylpyrrolidone,

[0198] -quaternized N,N-dimethylaminomethacrylate,

[0199] -diallyldimethylammonium chloride,

[0200] -Quaternized vinyl imidazole (3-methyl-1-vinyl-1H-imidazol-3-ium chloride)

[0201] -acrylamidopropyltrimonium chloride,

[0202] -Cassia hydroxypropyltrimonium chloride,

[0203] - Guar hydroxypropyltrimonium chloride or 25-polygalactomannan 2-hydroxypropyltrimonium chloride ether,

[0204] - Starch hydroxypropyltrimonium chloride and cellulose hydroxypropyltrimonium chloride,

[0205] - Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-10, Polyquaternium-11, Polyquaternium-16, Polyquaternium-22, Polyquaternium-28, Polyquaternium-43, Polyquaternium-44, Polyquaternium-46.

[0206] Examples of suitable nonionic surfactants include, but are not limited to

[0207] -Polycondensation product of ethylene oxide and propylene oxide

[0208] o Compounds based on ethylene oxide and propylene oxide having an average molar mass of 200 to 10 000 g / mol and preferably 1000 to 4000 g / mol, wherein the mass proportion of polyethoxylated blocks varies between 10% and 80%.

[0209] - Polycondensates of ethylene oxide and / or propylene oxide with fatty alcohols

[0210] ο Polyethylene glycol ethers of branched or linear alcohols

[0211] o Polypropylene glycol ethers of branched or linear alcohols

[0212] o Polycondensates of polyethylene glycol ethers and polypropylene glycol ethers of branched or linear alcohols, in which the polyethylene and polypropylene portions of the surfactant may be grafted adjacent to each other, or they may be randomly interspersed.

[0213] o terminal-capped and non-terminal-capped alkoxylated linear and branched, saturated and unsaturated alcohols (e.g. butoxy polyethylene glycol-polypropylene glycol),

[0214] - Condensation products of ethylene oxide and / or propylene oxide with fatty acids

[0215] o Reaction products of fatty acids or fatty acid alcohols with ethylene oxide and / or propylene oxide

[0216] - polycondensates of ethylene oxide and / or propylene oxide with phenol, substituted phenols (preferably alkylphenols or arylphenols): for example tristyrylphenol ethoxylates or alkylarylpolyglycol ethers or nonylphenol ethoxylates

[0217] - Condensation products of ethylene oxide and / or propylene oxide with fatty amines

[0218] - Polyoxyethylene fatty acid esters, such as castor oil ethoxylate

[0219] -Polyoxyethylene fatty alcohol ether

[0220] - fatty esters of polyols (for example fatty acid esters of glycerol, sorbitol or sucrose) and ethoxylates thereof, for example esters of polyglycerol ethoxylates or esters of ethoxylated sorbitol

[0221] - Fatty esters of alkanolamides

[0222] -Methylcellulose

[0223] -Polyvinyl alcohol

[0224] -Polyvinylpyrrolidone

[0225] οPolymer of PVP and dimethylaminoethyl methacrylate

[0226] οButyl PVP

[0227] -Polyvinyl alcohol and polyvinyl pyrrolidone copolymer

[0228] -Copolymer of (meth)acrylic acid and (meth)acrylate

[0229] -Polyoxyalkyleneamine

[0230] -Polyoxyethylene glycol

[0231] - polyoxyethylene acetylene glycol and / or polyoxypropylene acetylene glycol

[0232] -Copolymers of vinyl chloride with vinyl acetate and partially hydrolyzed vinyl acetate

[0233] - Modified cellulose type

[0234] -Alkyl polyglucoside

[0235] Examples of suitable amphoteric surfactants include, but are not limited to

[0236] -Aminopropionate and iminodipropionate

[0237] - imidazoline derivatives, such as amphodiacetates, amphodiapropionates, amphohydroxypropylsulfonates

[0238] -Betaine

[0239] -Sultaine

[0240] -Phosphobetaine

[0241] -Amine oxides.

[0242] Rheology Control Agents c) (Thickeners / Modifiers)

[0243] As used herein, the term "rheology modifier" refers to substances known in the art to stabilize dispersions of active ingredients by affecting the rheological properties of the dispersion.

[0244] In addition, the preparations and the use forms obtained therefrom may also include as additional auxiliaries adhesives / rheology modifiers / thickeners, such as carboxymethylcellulose, and natural and synthetic polymers (such as gum arabic, polyvinyl alcohol and polyvinyl acetate) in the form of powders, granules or latexes, or natural phospholipids (such as cephalins and lecithins) and synthetic phospholipids. Other auxiliaries may be mineral oils and vegetable oils.

[0245] Suitable rheology modifiers, thickeners are, for example,

[0246] - Polysaccharides include xanthan gum, guar gum and hydroxyethyl cellulose. Examples are G and 23, CX911 and 250 Series.

[0247] - Clays include montmorillonite, bentonite, sepiolite, attapulgite, laponite, hectorite. Examples are R. Van B. CT, HC, EW, M100, M200, M300, S, M, W, 50. RD,

[0248] - Hydrophylic silica and precipitated hydrophilic silica, examples of which are 200, 380, twenty two.

[0249] - fumed hydrophobic silica and precipitated hydrophobic silica, examples of which are R812, R812S, R972

[0250] pH buffer d)

[0251] As used herein, the term "pH buffer" refers to a substance known in the art that is capable of maintaining a specified pH in an aqueous solution. Examples of such buffers are listed in the Canadian Research Council (CRC) Handbook of Chemistry and Physics (ISBN: 1-4987-5428-7).

[0252] Preferred are acetic acid, citric acid, formic acid, phosphoric acid and sulfuric acid.

[0253] Acetic acid and citric acid are more preferred.

[0254] Most preferred is citric acid.

[0255] Defoaming agent e)

[0256] As used herein, the term "defoaming agent" refers to a substance known in the art that is capable of preventing excessive foaming of a formulation during preparation and / or application by a consumer. Suitable defoaming properties are those that allow the agrochemical formulation to maintain the FAO limit for foam persistence specified in CIPAC Method 47.3 throughout its shelf life.

[0257] Suitable antifoams are all substances which can usually be used for such purposes in agrochemical compositions.

[0258] Silicone oil and magnesium stearate are preferred.

[0259] Biocides f)

[0260] As used herein, the term "biocide" refers to substances known in the art that are capable of preventing the growth of microorganisms / fungi in water-based formulations.

[0261] Suitable preservatives are all substances which are usually used for such purposes in agrochemical compositions of this type.

[0262] Suitable biocides are preservatives such as dichlorophenol and benzyl alcohol hemiformal, 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 D7 (Lanxess), CG / ICP(Dow), SPX (Thor GmbH) and GXL (Arch Chemicals).

[0263] Antifreeze g)

[0264] Suitable antifreeze agents and low-temperature stabilizers are, for example, propylene glycol, ethylene glycol, urea, glycerol, inorganic salts (for example sodium chloride, potassium chloride, sodium sulfate, potassium sulfate).

[0265] Carrier h):

[0266] Suitable extenders / carriers are, for example, water, polar and nonpolar organic chemical liquids, for example from the following classes: aromatic and nonaromatic hydrocarbons (for example paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which, if appropriate, may also be substituted, etherified and / or esterified), ketones (for example acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides, lactams (for example N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (for example dimethyl sulfoxide).

[0267] If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Useful liquid solvents are essentially: aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes; chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffins, such as mineral oil fractions, mineral oils and vegetable oils; alcohols, such as butanol or ethylene glycol and their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, which can all be added to the water.

[0268] Examples of suitable liquid extenders / carriers / solvents include, but are not limited to, water, organic solvents, and combinations thereof. Examples of suitable liquid extenders / carriers / solvents include polar and non-polar organic chemical liquids, such as from the following categories:

[0269] - aromatic and non-aromatic hydrocarbons (for example cyclohexane, paraffins, alkylbenzenes, xylenes, toluene, tetralin, alkylnaphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons (for example chlorobenzene, vinyl chloride or methylene chloride)),

[0270] - alcohols and polyols (which may also be optionally substituted, etherified and / or esterified, for example ethanol, propanol, butanol, benzyl alcohol, cyclohexanol or ethylene glycol, 2-ethylhexanol),

[0271] -ethers, e.g.

[0272] oDioctyl ether, tetrahydrofuran, dimethyl isosorbide, solketal, cyclopentyl methyl ether, dibenzyl ether

[0273] o Dow’s Dowanol glycol ether products, or various grades of polyethylene glycol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, triethylene glycol monobenzyl ether),

[0274] o Polypropylene glycol ethers of different grades (e.g. propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, dipropylene glycol monobenzyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether, tripropylene glycol monobenzyl ether)

[0275] οAnisole, phenethyl ether

[0276] οDimethyl polyethylene glycol of different molecular weight grades, dimethyl polypropylene glycol of different molecular weight grades,

[0277] - ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, acetophenone, propiophenone),

[0278] - esters (also including methylated fats and oils, for example rapeseed oil methyl ester, soybean oil methyl ester, coconut oil methyl ester, 2-ethylhexyl palmitate, 2-ethylhexyl stearate), for example butyl propionate, amyl propionate, methyl caproate, methyl caprylate, methyl caprate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, isobornyl acetate, benzyl benzoate, butyl benzoate, isopropyl benzoate,

[0279] - Di- / tri-esters, for example dimethyl succinate, dimethyl glutarate, dimethyl adipate, diisopropyl adipate, dibutyl adipate, benzyl-2-ethylhexyl adipate, dimethyl 2-methylglutarate, monoacetin, diacetin, triacetin, trimethyl citrate, triethyl citrate, acetylcitrate triethyl, tributyl citrate, acetylcitrate tributyl, and mixtures and blends thereof

[0280] - Lactic acid esters, such as methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethylhexyl lactate

[0281] - (Poly)ethers, such as polyethylene glycol of different molecular weight grades, polypropylene glycol of different molecular weight grades

[0282] - Unsubstituted and substituted amines

[0283] -amides (e.g. dimethylformamide, or N,N-dimethyllactamide, or N-formylmorpholine, or fatty acid amides, such as N,N-dimethyldecanamide or N,N-dimethyldec-9-ene-amide) and esters thereof, such as 6-(dimethylamino)-2-methyl-6-oxo-hexanoic acid methyl ester

[0284] - lactam (e.g. 2-pyrrolidone, or N-alkylpyrrolidone, such as N-methylpyrrolidone, or N-butylpyrrolidone, or N-octylpyrrolidone, or N-dodecylpyrrolidone, or N-methylcaprolactam, N-alkylcaprolactam)

[0285] - Lactones (e.g., γ-butyrolactone, γ-valerolactone, δ-valerolactone, or α-methyl γ-butyrolactone)

[0286] - sulfones and sulfoxides (for example dimethyl sulfoxide),

[0287] -Oils of vegetable or animal origin, such as sunflower oil, rapeseed oil, corn oil

[0288] - nitriles, for example linear or cyclic alkylnitriles, in particular acetonitrile, cyclohexanecarbonitrile, octanonitrile, dodecanonitrile.

[0289] - linear and cyclic carbonates, for example dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and its isomers, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, propylene carbonate, glycerol carbonate, butylene carbonate, pentylene carbonate, hexylene carbonate and octylene carbonate.

[0290] - Phosphoric acid esters, such as triethyl phosphate, tributyl phosphate, triisobutyl phosphate, trioctyl phosphate, tri(2-ethylhexyl) phosphate

[0291] - White mineral oil

[0292] - mixtures of any of the above, for example

[0293] o Ester mixtures, such as Rhodiasolv RPDE,

[0294] oMixtures of morpholine derivatives and cyclic carbonates, such as Armid FMPC

[0295] o Mixtures of dimethyl sulfoxide with esters and / or glycerol derivatives

[0296] The most preferred carrier is water.

[0297] Other adjuvants and auxiliary agentsi)

[0298] As mentioned above, other adjuvants and auxiliary components i) may be present, which are selected from adhesives, tackifiers, colorants, antioxidants, light stabilizers (especially UV stabilizers), other agents to improve chemical and / or physical stability, butylated hydroxytoluene [3.5-di-tert-butyl-4-hydroxytoluene, CAS No. 128-37-0], fragrances, protective colloids, binders, penetrants, retention promoters, stabilizers, chelating agents, complexing agents, humectants, spreading agents / wetting agents and gibberellins.

[0299] Suitable penetrants in the context of the present invention are all substances which are usually used to improve the penetration of agrochemical active compounds into plants. A penetrant is defined in the context of the present invention as its ability to penetrate from the (usually aqueous) application liquid and / or spray coating into the plant epidermis and thus to improve the mobility of the active compound in the epidermis. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used to determine this property. Examples include alcohol alkoxylates, for example coconut fat ethoxylate (10) or isotridecyl ethoxylate (12); fatty acid esters, for example rapeseed oil methyl ester or soybean oil methyl ester; fatty amine alkoxylates, for example tallowamine (tallowamine) ethoxylate (15); or ammonium and / or phosphonium salts, for example ammonium sulfate or diammonium hydrogen phosphate.

[0300] Suitable penetration enhancers are, for example:

[0301] - ethoxylated linear and / or branched fatty alcohols (e.g. Clariant's X-type), which has 2-20 EO units;

[0302] - methyl-terminated ethoxylated linear and / or branched fatty alcohols (e.g. Clariant's XM type), which contains 2-20 EO units;

[0303] - Ethoxylated coconut alcohol (e.g. Clariant's Type C), which contains 2-20 EO units;

[0304] - Ethoxylated C12 / 15 alcohols (e.g. Croda's Type A), which contains 2-20 EO units;

[0305] -propoxylated-ethoxylated alcohols, branched or linear, such as Solvay's B / 848, Croda G5000, Levaco HOT 5902, Evonik’s Break-Thru Vibrant;

[0306] - Propoxylated-ethoxylated fatty acids, methyl terminated, such as Lion's OC0503M;

[0307] - Alkyl ether citrate surfactants (e.g. Adsee CE series, Akzo Nobel);

[0308] -Alkyl polysaccharides (e.g. BASF's PG8107, PG8105; Croda 438, AL-2559, AL-2575);

[0309] - ethoxylated mono- or diesters of glycerol containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 40 EO units (e.g. Croda's product line);

[0310] - castor oil ethoxylates containing on average 5 to 40 EO units (e.g. castor oil ethoxylates of Nouryon Series, Clariant EL series);

[0311] - Block copolymers of polyethylene oxide and polypropylene oxide (for example the Pluronic series from BASF).

[0312] -Oils used as penetration enhancers are all oils of vegetable, mineral and animal origin which are usually used in agrochemicals. Examples are:

[0313] οSunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, olive oil;

[0314] oSunflower oil methyl ester, rapeseed oil methyl ester, corn oil methyl ester, soybean oil methyl ester, rice bran oil methyl ester, olive oil methyl ester

[0315] o Linear and / or branched alkyl esters of C10-C24 saturated fatty acids of plant or mineral origin: for example methyl, ethyl, propyl, butyl, amyl, hexyl, isopropyl, isobutyl, isopentyl, 2-ethylhexyl esters of decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid.

[0316] o Linear and / or branched alkyl esters of C10-C24 unsaturated fatty acids of plant or mineral origin: for example methyl, ethyl, propyl, butyl, amyl, hexyl, isopropyl, isobutyl, isopentyl, 2-ethylhexyl esters of α-linolenic acid, linoleic acid, trans-linoleic acid, palmitoleic acid, oleic acid, erucic acid.

[0317] o White paraffinic mineral oil, such as Shell's series.

[0318] oA mixture of two or more of the above

[0319] Useful retention promoters include all those substances which reduce the dynamic surface tension, such as dioctyl sulfosuccinate, or which increase the viscoelasticity, such as hydroxypropyl guar polymers.

[0320] Suitable wetting agents, spreading agents and / or retaining agents are, for example:

[0321] - ethoxylated branched alcohols (e.g. X-type), which contains 2-20 EO units;

[0322] - methyl terminated ethoxylated branched alcohols (e.g. XM type), which contains 2-20 EO units;

[0323] -propoxylated-ethoxylated alcohols, branched or linear, e.g. B / 848, G5000, HOT 5902;

[0324] -Organo-modified polysiloxanes, e.g. OE444, S240, L77、Silwet 312、 408, 806;

[0325] - monoesters and diesters of sodium sulfosuccinate with branched or linear alcohols containing 1 to 10 carbon atoms, for example Geropon DOS;

[0326] - ethoxylated diacetylenediols, for example 4xx series;

[0327] For the treatment of seeds in particular, colorants are often used.

[0328] Colorants that may be present in the seed dressing formulations which can be used according to the invention are all colorants usually used for such purposes. It is possible to use sparingly water-soluble pigments or water-soluble dyes. Examples include the dyes known by the names Rhodamine B ([9-(2-carboxyphenyl)-6-(diethylamino)xanthene-3-ylidene]-diethylazepinium; chloride), CI Pigment Red 112 (3-hydroxy-N-(2-methylphenyl)-4-[(2,4,5-trichlorophenyl)diazenyl]naphthalene-2-carboxamide) and CI Solvent Red 1 (1-[(2-methoxyphenyl)diazenyl]naphthalene-2-ol).

[0329] Useful wetting agents that may be present in the seed dressing formulations which can be used according to the invention are all substances which promote wetting and which are customarily used for formulating agrochemically active compounds. Preference is given to using alkylnaphthalenesulfonates, for example diisopropylnaphthalenesulfonate or diisobutylnaphthalenesulfonate.

[0330] Adhesives which may preferably be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in seed dressing products. Polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, acrylic acid, styrene butadiene polymers and methyl cellulose (tylose) may be mentioned as preferred.

[0331] Gibberellins which may preferably be present in the seed dressing formulations which can be used according to the invention are preferably gibberellins A1, A3 (=gibberellic acid), A4 and A7; gibberellic acid is particularly preferably used. Gibberellins are known (cf. R. Wegler "Chemie der Pflanzenschutz-and 2, Springer Verlag, 1970, pp. 401-412).

[0332] Other active substances k)

[0333] The active compounds identified herein by their common names are known and described, for example, in the Pesticide Manual ("The Pesticide Manual" 16th edition, 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 this patent application.

[0334] In a preferred embodiment, the one or more further active substances are selected from the group consisting of insecticides / acaricides and nematicides.

[0335] Preferably, it is selected from:

[0336] (1) an acetylcholinesterase (AChE) inhibitor, preferably a carbamate selected from the group consisting of alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathi ocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or an organophosphate selected from acephate, azamethiphos, acetyl methionine, thiophene amine ... azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos hos), 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, methyl pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon and vamidothion.

[0337] (2) GABA-gated chloride channel blockers, preferably cyclodiene-organochlorines selected from chlordane and endosulfan, or from phenylpyrazoles (fiproles) selected from ethiprole and fipronil.

[0338] (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, β-cyfluthrin , cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(1R)-trans-isomer], deltamethrin, empenthrin [(EZ)-(1R)-isomer], esfenvalerate, etofenp rox), fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin thrin) [(1R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer], tralomethrin and transfluthrin or DDT or methoxychlor.

[0339] (4) Competitive modulators of nicotinic acetylcholine receptors (nAChR), 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.

[0340] (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators (site I), preferably spinosyns, selected from spinetoram and spinosad.

[0341] (6) Glutamate-gated chloride channel (GluCl) allosteric modulators, preferably avermectins / milbemycins selected from abamectin, emamectin benzoate, lepimectin and milbemectin.

[0342] (7) Juvenile hormone mimetics, preferably selected from the following juvenile hormone analogs: hydroprene, kinoprene and methoprene, or fenoxycarb or pyriproxyfen.

[0343] (8) Various non-specific (multi-site) inhibitors, preferably alkyl halides selected from methyl bromide and other alkyl halides; or chloropicrine or sulfuryl fluoride or borax or tartar emetic, or methyl isocyanate generators selected from diazomet and metam.

[0344] (9) String organ TRPV channel modulators, preferably pyridinyl azomethanes selected from pymetrozine and pyrifluquinazone; or pyropenes selected from afidopyropen.

[0345] (10) A mite growth inhibitor affecting CHS1 selected from clofentezine, hexythiazox, diflovidazin and etoxazole.

[0346] (11) An insect intestinal membrane microbial disruptor selected from Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis and a Bt plant protein selected from the following: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb and Cry34Ab1 / 35Ab1.

[0347] (12) Mitochondrial ATP synthase inhibitors, preferably ATP disruptors selected from diafenthiuron; or organotin compounds selected from azocyclotin, cyhexatin and fenbutatinoxide; or propargite or tetradifon.

[0348] (13) An uncoupler of oxidative phosphorylation by interrupting the proton gradient, selected from chlorfenapyr, DNOC and sulfluramid.

[0349] (14) A nicotinic acetylcholine receptor channel blocker selected from the group consisting of bensultap, cartap hydrochloride, thiocylam and thiosultap-sodium.

[0350] (15) Chitin biosynthesis inhibitors affecting CHS1, preferably benzoyl ureas, selected from bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.

[0351] (16) Chitin biosynthesis inhibitors, type 1, selected from buprofezin.

[0352] (17) Molting disruptors (especially for Diptera, i.e. insects of the order Diptera) selected from cyromazine.

[0353] (18) Ecdysone receptor agonists, preferably diacylhydrazine selected from chromafenozide, halofenozide, methoxyfenozide and tebufenozide.

[0354] (19) An octopamine receptor agonist selected from amitraz.

[0355] (20) A mitochondrial complex III electron transport inhibitor selected from the group consisting of hydramethylnone, acequinocyl, fluacrypyrim and bifenazate.

[0356] (21) Mitochondrial complex I electron transport inhibitors, preferably METI acaricides and insecticides selected from fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad, or rotenone (Derris).

[0357] (22) Voltage-dependent sodium channel blockers, preferably oxadiazines selected from indoxacarb, or semicarbazones selected from metaflumizone.

[0358] (23) Acetyl-CoA carboxylase inhibitors, preferably tetronic acid and tetramic acid derivatives selected from spirodiclofen, spiromesifen, spiropidion and spirotetramat.

[0359] (24) Mitochondrial complex IV electron transport inhibitors, preferably phosphides selected from aluminum phosphide, calcium phosphide, phosphine and zinc phosphide; or cyanides selected from calcium cyanide, potassium cyanide and sodium cyanide.

[0360] (25) Mitochondrial complex II electron transport inhibitors, preferably β-ketonitrile derivatives selected from cyenopyrafen and cyflumetofen; or carboxanilides selected from pyflubumide.

[0361] (28) ryanodine receptor modulators, preferably diamides selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide and tetraniliprole.

[0362] (29) A chord organ modulator (with an unclear target site) selected from flonicamid.

[0363] (30) GABA-gated chloride channel allosteric modulators, preferably diamides selected from broflanilide; or isoxazoles selected from fluxametamide.

[0364] (31) Baculovirus, preferably a granulovirus (GV) selected from the group consisting of Cydia pomonella GV and Thaumatotibia leucotreta (GV), or a nuclear polyhedrosis virus (NPV) selected from the group consisting of Anticarsia gemmatalis MNPV, Flucypyriprol and Helicoverpa armigera NPV.

[0365] (32) A nicotinic acetylcholine receptor allosteric modulator (site II) selected from the group consisting of GS-ω / κHXTX-Hv1a peptide.

[0366] (33) Other active compounds selected from the group consisting of: 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 (CAS1771741-86-6), Fluensulfone, Flufenerim, Flufenoxystrobin, Flufipro le), Fluhexafon, Fluopyram, Flupyrimin, Fluralaner, Fufenozide, Flupentiofenox, Guadipyr, Heptafluthrin, Imidaclothiz, Iprodione, Isocycloseram, Kappa-Bifenthrin, Kappa-Tefluthrin, Lotilaner, Meperfluthrin, Nicofluprole (CAS1771741-86-6), Oxazosulfyl, Paichongding, Pyridalyl, Pyrifluquinazon, Pyriminostrobin, Sarolaner, Spidoxamat, Spirobudiclofen, Tetramethylfluthrin, Tetrachlorantraniliprole, Tigolaner, Tioxazafen, Thiofluoximate, Tyclopyrazoflor, Methyl iodide; In addition, there are Bacillus firmus-based firmus) (1-1582, Votivo) and azadirachtin (BioNeem), and the following compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO2006 / 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 WO2006 / 003494) (CAS 872999-66-1), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-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-1,8-diazaspiro[4.5]dec-3-en-4-yl carbonate (known from EP 2647626) (CAS1440516-42-6), PF1364 (known from JP2010 / 018586) (CAS1204776-60-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1,1,1-trifluoro-propan-2-one (known from WO2013 / 144213) (CAS1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO2010 / 051926) (CAS1226889-14-0), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3 -chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxo-3-thietanyl)-benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxo-3-thietanyl)-benzamide, 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxo-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxo-3-thietanyl)benzamide (by WO 2013 / 050317 A1) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propionamide, (+)-N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propionamide and (-)-N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propionamide (known from WO 2013 / 162715 A2, WO 2013 / 162716A2, US2014 / 0213448 A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (known from CN 101337937 A) (CAS1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thiomethyl]phenyl]-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide, (thiobenzamide (Liudaibenjiaxuanan), known from CN 103109816 A) (CAS 1232543-85-9), N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known from WO 2012 / 034403 A1 known) (CAS 1268277-22-0), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (known from WO 2011 / 085575 A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-dichloro-2-propen-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN 101337940 A known from CAS 1108184-52-6), (2E)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide (known from CN 101715774 A) (CAS 1232543-85-9), 3-(2,2-dichlorovinyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl-cyclopropanecarboxylate (known from CN 103524422 A known) (CAS 1542271-46-4), (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]-indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN 102391261 A) (CAS 1370358-69-2), 6-deoxy-3-O-ethyl-2,4-di-O-methyl-, 1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,4-triazol-3-yl]phenyl]carbamate]-α-L-pyranose (known from US 2014 / 0275503 A1) (CAS1181213-14-8), 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 1253850-56-4), (8-trans)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 933798-27-7), (8-cis)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (WO2007040280A1, WO 2007040282 A1) (CAS 934001-66-8), N-[4-(aminothiomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (known from CN 103265527 A) (CAS 1452877-50-7), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dione (known from WO 2014 / 187846A1) (CAS1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl-carbonic acid ethyl ester (known from WO 2010 / 066780A1, WO 2011151146 A1) (CAS1229023-00-0), N-[1-(2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO 2014 / 053450 A1) (CAS 1594624-87-9), N-[2-(2,6-difluorophenyl)-2H-1,2,3-triazol-4-yl]-2-(trifluoromethyl)benzamide (known from WO 2014 / 053450 A1) (CAS 1594637-65-6), N-[1-(3,5-difluoro-2-pyridyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO 2014 / 053450 A1) (CAS 1594626-19-3), (3R)-3-(2-chloro-5-thiazolyl)-2,3-dihydro-8-methyl-5,7-dioxo-6-phenyl-5H-thiazolo[3,2-a]pyrimidinium ide (known from WO 2018 / 177970 A1 Known)(CAS2246757-58-2), 3-(2-chloro-5-thiazolyl)-2,3-dihydro-8-methyl-5,7-dioxo-6-phenyl-5H-thiazolo[3,2-a]pyrimidinium ide (known from WO 2018 / 177970 A1) (CAS 2246757-56-0), N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-2-(methylsulfonyl)-propionamide (known from WO 2019 / 236274 A1) (CAS 2396747-83-2), N-[2-bromo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-2-fluoro-3-[(4-fluorobenzoyl)amino]-benzamide (known from WO 2019 / 236274 A1) (CAS 2396747-83-2), 2019059412 A1 known) (CAS 1207977-87-4), 3-bromo-1-(3-chloro-2-pyridyl)-N-[4,6-dichloro-3-fluoro-2-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide (Fluchlorodiamide; known from CN110835330A, CN106977494A) (CAS: 2129147-03-9).

[0367] In another preferred embodiment, the one or more other active substances are fungicides, which are preferably selected from:

[0368] 1) Inhibitors of ergosterol biosynthesis, such as (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenbuconazole, (1.005) fenhexamid, (1.006) fenpropidin, (1.007) fenpropimorph, (1.008) fenpyrazamine, (1.009) fluquinconazole onazole), (1.010) flutriafol, (1.011) hexaconazole, (1.012) imazalil, (1.013) imazalil sulfate, (1.014) ipconazole, (1.015) ipfentrifluconazole, (1.016) mefentrifluconazole, (1.017) metconazole, (1.018) myclobutanil, (1.019) paclobutrazol clobutrazol), (1.020) penconazole, (1.021) prochloraz, (1.022) propiconazole, (1.023) prothioconazole, (1.024) pyrisoxazole, (1.025) spiroxamine, (1.026) tebuconazole, (1.027) tetraconazole, (1.028) triadimenol, (1.02 9) tridemorph, (1.030) triticonazole, (1.031) (1R, 2S, 5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.032) (1S, 2R, 5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.033) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.034)034) (2R) -2- (1-chlorocyclopropyl) -4- [(1S) -2,2-dichlorocyclopropyl] -1- (1H-1,2,4-triazol-1-yl) butan-2-ol, (1.035) (2R) -2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1H-1,2,4-triazol-1-yl) propan-2-ol, (1.036) (2S) -2- (1-chlorocyclopropyl) -4- [(1R) -2,2-dichlorocyclopropyl] -1- (1H-1,2,4-triazol-1-yl) butan-2-ol, (1.037) (2S) -2- (1-chlorocyclopropyl) -4- [(1S) -2,2-dichlorocyclopropyl] -1- (1H -1,2,4-triazol-1-yl)butan-2-ol, (1.038) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.039) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.040) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.041) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1 ,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.042) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.043) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.044) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazol-5-ylthiocyanate, ( 1.045) 1-{[rel (2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.046) 1-{[rel (2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.047) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethyl-hept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.048)048) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.050) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2- [(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethyl-hept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.052) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethyl-hept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.053) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethyl-hept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.054) 2-[(2S,4 S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.055) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.056) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.057) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol ) propan-2-ol, (1.058) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 2-{[relative to (2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.060) 2-{[relative to (2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxirane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.061) 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, (1.062) 4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]-benzonitrile, (1.063) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.064) 5-(allylsulfanyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane -2-yl]methyl}-1H-1,2,4-triazole, (1.065) 5-(allylsulfanyl)-1-{[relative to (2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazole, (1.066) 5-(allylsulfanyl)-1-{[relative to (2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluoro-phenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazole, (1.067) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propanoic acid methyl ester, (1.0 68) N'-(2-chloro-5-methyl-4-phenoxyphenyl]-N-ethyl-N-methyliminocarboxamide, (1.069) N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methyliminocarboxamide, (1.070) N'-[5-bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methyliminocarboxamide, (1.071) N'-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methyliminocarboxamide, (1.072) N'-{5-bromo-2-methyl-6-[ (1-propoxyprop-2-yl)oxy]pyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.073) N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methyl-pyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.074) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.075) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.076)076) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.077) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarboxamide, (1.078) N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methyliminocarboxamide. .

[0369] 2) Inhibitors of respiratory complex I or II, for example (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) cyclobutrifluram, (2.006) flubeneteram, (2.007) fluindapyr, (2.008) fluopyram, (2.009) flutolanil 、(2.010) fluxapyroxad、(2.011) furametpyr、(2.012) inpyrfluxam、(2.013) isofetamid、(2.014) isoflucypram、(2.015) isopyrazam、(2.016) penflufen、(2.017) penthiopyrad、(2.018) pydiflumetofen、(2.019) pyrimidine amide (pyrapropoyne), (2.020) pyraziflumid, (2.021) sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide formamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.029) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.030) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.031) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.032) N-[(1R,4S)-9-(dichloro-methylene)-1,2,3,4-tetrahydro-1,4-bridged Methylenenaphthalene (methanonaphthalen)-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.033) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-bridged methylenenaphthalene-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.034) N-[1-(2,4-dichlorophenyl)-1-methoxyprop-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-[rac-(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide. .

[0370] 3) Inhibitors of respiratory complex III, such as (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) oxathiapiprolin, (3.010) oxathiapiprolin, (3.011) oxathiapiprolin, (3.012) oxathiapiprolin, (3.013) oxathiapiprolin, (3.014) oxathiapiprolin, (3.015) oxathiapiprolin, (3.016) oxathiapiprolin, (3.017) oxathiapiprolin, (3.018) oxathiapiprolin, (3.019) oxathiapiprolin, (3.020) oxathiapiprolin, (3.021) oxathiapiprolin, (3.022) oxathiapiprolin, (3.023) oxathiapiprolin, (3.024) oxathiapiprolin, (3.025) oxathiapiprolin, (3.026) oxathiapiprolin amoxadone), (3.010) fenamidone, (3.011) fenpicoxamid, (3.012) florylpicoxamid, (3.013) flufenoxystrobin, (3.014) fluoxastrobin, (3.015) kresoxim-methyl, (3.016) mandestrobin, (3.017) metominostrobin, (3.018) metyltetracycline prole), (3.019) orysastrobin, (3.020) picoxystrobin, (3.021) pyraclostrobin, (3.022) pyrametostrobin, (3.023) pyraoxystrobin, (3.024) trifloxystrobin, (3.025) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl] phenyl}-2-(methoxyimino)-N-methylacetamide, (3.026) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.027) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.028) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.029) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-carboxamido-2-hydroxybenzamide, (3.030)030)(2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.031){5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamic acid methyl ester. .

[0371] 4) Mitosis and cell division inhibitors, for example (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) fluopimomide, (4.006) metrafenone, (4.007) pencycuron, (4.008) pyridachlometyl, (4.009) pyriofenone (chlazafen one), (4.010) thiabendazole, (4.011) thiophanate-methyl, (4.012) zoxamide, (4.013) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.014) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.016) 4-(2-bromo-4- 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.020) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.0 21) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.023) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.026)026) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.027) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.028) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine. .

[0372] 5) Compounds capable of multi-site action, such as (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, oxychloride), (5.009) copper sulfate (2+), (5.010) dicyanoanthraquinone (dithianon), (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) metiram zinc zinc), (5.017) oxine-copper, (5.018) propineb, (5.019) sulfur and sulfur preparations including calcium polysulfide, (5.020) thiram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.

[0373] 6) Compounds capable of inducing host defense, such as (6.001) acibenzolar-S-methyl, (6.002) fosetyl-aluminum, (6.003) fosetyl-calcium, (6.004) fosetyl-sodium, (6.005) isotianil, (6.006) phosphorous acid and its salts, (6.007) probenazole, and (6.008) tiadinil.

[0374] 7) Inhibitors of amino acid and / or protein biosynthesis, for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil.

[0375] 8) Inhibitors of ATP production, for example (8.001) silthiofam.

[0376] 9) Inhibitors of cell wall synthesis, for example (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.

[0377] 10) Inhibitors of lipid synthesis or transport or membrane synthesis, for example (10.001) fluoxapiprolin, (10.002) natamycin, (10.003) oxathiapiprolin, (10.004) propamocarb, (10.005) propamocarb hydrochloride, hydrochloride), (10.006) propamocarb-fosetylate, (10.007) tolclofos-methyl, (10.008) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (10.009) 1-(4-{4 -[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (10.010) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (10.011) 2-[3, 5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (10.012) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (10.013) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (10.014) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (10.015) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (10.016) 3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (10.017) 9-fluoro-3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (10.018) 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (10.019) 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-9-fluoro-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate. .

[0378] 11) Melanin biosynthesis inhibitors, for example (11.001) tolprocarb, (11.002) tricyclazole.

[0379] 12) Nucleic acid synthesis inhibitors, for example (12.001) benalaxyl, (12.002) high-efficiency benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) high-efficiency metalaxyl-M (mefenoxam).

[0380] 13) Signal transduction inhibitors, for example, (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.

[0381] 14) Compounds that can act as uncouplers, for example (14.001) fluazinam, (14.002) meptyldinocap.

[0382] 15) Other compounds, such as (15.001) abscisic acid, (15.002) aminopyrifen, (15.003) benthiazole, (15.004) bethoxazin, (15.005) capsimycin, (15.006) carvone, (15.007) chinomethionat, (15.008) cufraneb, (15.009) cyflufenamid, (15.010) cymoxanil, (15.011 ) cyprosulfamide, (15.012) dipymetitrone, (15.013) flutianil, (15.014) ipflufenoquin, (15.015) methyl isothiocyanate, (15.016) mildiomycin, (15.017) nickel dimethyldithiocarbamate, (15.018) nitrothal-isopropyl, (15.019) oxyfenthi in, (15.020) pentachlorophenol and its salts, (15.021) picarbutrazox, (15.022) quinofumelin, (15.023) D-tagatose, (15.024) tebufloquin, (15.025) tecloftalam, (15.026) tolnifanide, (15.027) 2-(6-benzylpyridin-2-yl)quinazoline, (15.028) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.029) .029) 2-phenylphenol and its salts, (15.030) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.031) 4-oxo-4-[(2-phenylethyl)amino]butyric acid, (15.032) 5-amino-1,3,4-thiadiazole-2-thiol, (15.033) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene-2-sulfonylhydrazide, (15.034) 5-fluoro-2-[(4-fluorobenzyl)oxy]-pyrimidin-4-amine, (15.035) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.036)036) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.037) but-3-yn-1-yl {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.038) (2Z)-3-amino-2-cyano-3-phenylacrylate ethyl ester, (15.039) phenazine-1-carboxylic acid, (15.040) 3,4,5-trihydroxybenzoic acid propyl ester, (15.041) quinolin-8-ol, (15.042) quinolin-8-ol sulfate (2:1), (15 .043) 1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.044) 1-(5-(fluoromethyl)-6-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.045) 1-(5,6-dimethylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.046) 1-(6-(difluoromethyl)-5-methoxy-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.047) 1-(6-(difluoromethyl) -5-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.048) 1-(6,7-dimethylpyrazolo[l,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.049) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.050) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.051) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-8-fluoroquinoline, (1 5.052) 3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline, (15.053) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.054) 5-bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline, (15.055) 8-fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)-quinoline, (15.056) 8-fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-quinoline, (15.057) 8-Fluoro-N-(4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl)quinoline-3-carboxamide, (15.058) 8-Fluoro-N-[(2S)-4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl]quinoline-3-carboxamide, (15.059) 9-Fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.060) N-(2,4-dimethyl-1-phenylpentan-2-yl)-8-fluoroquinoline-3-carboxamide, (15.061) N-[(2S)-2,4-dimethyl-1-phenylpentan-2-yl]-8-fluoroquinoline -3-formamide, (15.062) 1,1-diethyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.063) 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.064) 1-[[3-fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]azepan-2-one, (15.065) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.066) 1-methoxy-1-methyl-3- [[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.067) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.068) 1-methoxy-3-methyl-1-[[4-[5-[(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.069) 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.070) 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.071) 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.072) 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.073) 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.074) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.076) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.077) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.078) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.079) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.080) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.081) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.082) 4-[075) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.076) 5-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.077) 1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-pyrazole-4-carboxylic acid ethyl ester, (15.078) methyl {4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}carbamate, (15.079) N-(1-methylcyclopropyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}carbamate 2,4-oxadiazol-3-yl]benzamide, (15.080) N-(2,4-difluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.082) N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.083) N,N-dimethyl-1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-1,2,4-triazol-3-amine, (15.084 )N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.085)N-[(E)-N-methoxy-C-methyl-carbonimido]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.086)N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.087)N-[(Z)-N-methoxy-C-methyl-carbonimido]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.088)N-[[2, 3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propionamide, (15.089) N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide, (15.090) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]cyclopropanecarboxamide, (15.091) N-{2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butanamide, (15.092) N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}cyclopropanecarboxamide, (15.093) N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}propanamide, (15.094) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide, (15.095) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.096) N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl ] propionamide, (15.097) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, (15.098) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.099) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide, (15.100) N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide. .

[0383] In another preferred embodiment, the other active substance is a biopesticide.

[0384] Biopesticides include, in particular, bacteria, fungi, yeasts, plant extracts and products formed by microorganisms (including proteins and secondary metabolites).

[0385] Biopesticides include bacteria such as spore-forming bacteria, root-colonizing bacteria, and bacteria used as bioinsecticides, fungicides, or nematicides.

[0386] Examples of such bacteria that can be used or used as biopesticides are:

[0387] Bacillus amyloliquefaciens, strain FZB42 (DSM 231179); or Bacillus cereus, in particular Bacillus cereus strain CNCM I-1562; or Bacillus firmus, strain I-1582 (accession number CNCM I-1582); or Bacillus pumilus, in particular strain GB34 (accession number ATCC 700814) and strain QST2808 (accession number NRRL B-30087); or Bacillus subtilis, in particular strain GB03 (accession number ATCC SD-1397), or Bacillus subtilis strain QST713 (accession number NRRL B-21661) or Bacillus subtilis strain OST 30002 (accession number NRRL Bacillus thuringiensis, in particular Bacillus thuringiensis subsp. israelensis (serotype H-14), strain AM65-52 (accession number ATCC 1276), or Bacillus thuringiensis subsp. ayuzawa, in particular strain ABTS-1857 (SD-1372), or Bacillus thuringiensis subsp. kustaki HD-1 or Bacillus thuringiensis subsp. pseudogaphage NB 176 (SD-5428); Pasteuria penetrans, Pasteuria spp. (Rotylenchulus reniformis nematode)-PR3 (accession number ATCC SD-5834); Streptomyces microflavus strain AQ6121 (=QRD 31.013, NRRL B-50550); Streptomyces galbus strain AQ 6047 (accession number NRRL 30232).

[0388] Examples of fungi and yeasts that may be used or may be used as biopesticides are:

[0389] Beauveria bassiana, in particular strain ATCC 74040; Coniothyrium minitans, in particular strain CON / M / 91-8 (accession number DSM-9660); Lecanicillium spp., in particular strain HRO LEC 12; Lecanicillium lecanii (formerly Verticillium leccmii), in particular strain KV01; Metarhizium anisopliae, in particular strain F52 (DSM3884 / ATCC 90448); Metschnikowia fructicola, in particular strain NRRL Y-30752; Paecilomyces fumosoroseus (now known as Isaria fumosorosea), in particular strain IFPC 200613 or strain Apopka 97 (accession number ATCC 20874); Paecilomyces lilacinus, in particular Paecilomyces lilacinus strain 251 (AGAL 89 / 030550); Talaromyces flavus, in particular strain V117b; Trichoderma atroviride, in particular strain SC1 (accession number CBS122089); Trichoderma harzianum, in particular Trichoderma harzianum T39 (accession number CNCM 1-952).

[0390] Examples of viruses that may be used or may be used as biopesticides are:

[0391] Adoxophyes orana (summer fruit tortrix) granulovirus (GV), Codling moth (codling moth) granulovirus (GV), Cotton bollworm (cotton bollworm) nuclear polyhedrosis virus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, Spodoptera littoralis (African cotton leafworm) NPV.

[0392] Also included are bacteria and fungi which are added to plants or plant parts or plant organs as "inoculants" and which, by virtue of their special properties, promote plant growth and plant health. Examples which may be mentioned are:

[0393] Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp. or Gigaspora monosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp., Streptomyces spp.

[0394] Examples of plant extracts and microbial products (including proteins and secondary metabolites) that can be used or can be used as biopesticides are:

[0395] Garlic (Allium sativum), Wormwood (Artemisia absinthium), Azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, Chitin, Armour-Zen, Dryopteris filix-mas, Horsetail (Equisetum arvense), Fortune Aza, Fungastop, Heads Up (Chenopodium quinoa saponinextract), Pyrethrum / Pyrethrins, Quassia amara, Quercus, Quillaja, Regalia, "Requiem TM "insecticides", rotenone, ryania / ryanodine, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaelum majus, Urtica dioica, Veratrin, Viscum album, extracts of the Brassicaceae family (especially rapeseed powder or mustard powder), and biological insecticidal / acaricidal active substances obtained from olive oil, especially unsaturated fatty acids / carboxylic acids with a carbon chain length of C16-C20 as active ingredients, for example contained in the trade name products.

[0396] In another embodiment, the compounds of formula (I) can be combined with a safener, such as benoxacor, cloquintocet (cloquintocet, cloquintocet-mexyl), cyometrinil, cyprosulfonamide, dichlormid, fenchlorazole (fenchlorazole, fenchlorazole-ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen (isoxadifen, isoxadifen-ethyl), mefenpyr (mefenpyr, mefenpyr-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4).

[0397] If the functional groups of all specified mixing partners are capable of forming salts with suitable bases or acids, they may optionally form salts with suitable bases or acids. Where applicable, all specified mixing partners may include tautomeric forms.

[0398] Preferred mixed compatibility agents are selected from β-cyfluthrin, deltamethrin, permethrin, transfluthrin, spiromesifen, Spidoxamat, ethiprole, fipronil, thiacloprid and tetrazolam.

[0399] The most preferred mixed compatibility agents are deltamethrin, transfluthrin, spiromesifen and Spidoxamat.

[0400] Furthermore, the present invention relates to the use of polymorphic form A of a compound of formula (1) for controlling animal pests. The term "control" means inhibiting the development of animal pests (including mortality, reduced feeding and / or interference with mating). Surprisingly, it has been found that although the water solubility of polymorphic form A is 60% of that of polymorphic form B, the systemic biological efficacy of polymorphic form A is at the same level as the systemic biological efficacy of polymorphic form B.

[0401] In a specific embodiment, the present invention relates to controlling animal pests in crops of useful plants, including cereals (wheat, rice, triticale, barley, rye, oats), corn, soybeans, potatoes, beets, sugar cane, tomatoes, peppers, cucumbers, melons, carrots, watermelons, onions, lettuce, spinach, leeks, beans, Brassica oleracea (e.g. cabbage) and other vegetable species, cotton, tobacco, rapeseed and fruit plants (including fruits apples, pears, citrus fruits and grapevines). In a particularly preferred embodiment, the useful plants are fruits and grapes, vegetables and flowers, coffee and cocoa (plantations), potatoes, cotton, cereals, beets, rapeseed, corn and soybeans. In another specific embodiment of the invention, the useful plants are transgenic plants.

[0402] The invention also relates to a method for controlling animal or microbial pests, wherein the crystalline form A of the compound of formula (I) or a plant protection agent as defined above containing the crystalline form A of the compound of formula (I) is allowed to act on the animal or microbial pests and / or their habitat.

[0403] The control of animal pests is preferably carried out in agriculture and forestry and in the protection of materials. Methods for the surgical or therapeutic treatment of the human or animal body and diagnostic methods on the human or animal body are preferably excluded from this.

[0404] In another embodiment, the present invention relates to the use of the crystalline form A of the compound of formula (I) for controlling animal pests. The crystalline form A of the compound of formula (I) can be advantageously used as a pesticide, in particular a plant protection agent as described above. Preferably, the use in methods for surgical or therapeutic treatment of the human or animal body and in diagnostic methods performed on the human or animal body is excluded.

[0405] In the context of the present application, the term "pesticide" always also includes the term "plant protection agent" in each case.

[0406] All plants and plant parts can be processed according to the present invention. Herein, plants are understood to mean all plants and plant parts, such as desired and unwanted wild plants or crop plants (including naturally occurring crop plants), such as cereals (wheat, rice, triticale, barley, rye, oats), corn, soybeans, potatoes, beets, sugar cane, tomatoes, peppers, cucumbers, melons, carrots, watermelons, onions, lettuce, spinach, leeks, beans, cabbage (such as cabbage) and other vegetable species, cotton, tobacco, rapeseed and fruit plants (including fruit apples, pears, citrus fruits and grapevines). Crop plants can be plants that can be obtained by conventional breeding and optimization methods or by biotechnology and genetic engineering methods or a combination of these methods, including transgenic plants, and including plant varieties that can or cannot be protected by variety property rights. Plants are understood to mean all developmental stages, such as seeds, seedlings, young plants (immature) plants until mature plants. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as buds, leaves, flowers and roots, examples being leaves, needles, stalks, stems, flowers, fruiting bodies, fruits and seeds, as well as tubers, roots and rhizomes. Plant parts also include harvested plants or harvested plant parts and vegetative and generative propagation material, such as seedlings, tubers, rhizomes, cuttings and seeds.

[0407] According to the invention, the treatment of plants and plant parts with the crystalline form A of the compound of formula (I) is carried out directly or by allowing the compound to act on the surroundings, environment or storage space by conventional treatment methods, for example by soaking, spraying, evaporation, atomization, broadcasting, coating, injection, and in the case of propagation materials, in particular seeds, also by applying one or more coatings.

[0408] As mentioned above, all plants and their parts can be processed according to the present invention. In a preferred embodiment, wild plant species and plant cultivars, or those plants obtained by conventional biological breeding methods (such as hybridization or protoplast fusion), and their parts are processed. In another preferred embodiment, transgenic plants and plant cultivars (genetically modified organisms) and their parts obtained by genetic engineering methods (if appropriate, combined with traditional methods) are processed. The term "parts" or "parts of plants" or "plant parts" has been explained above. The present invention is particularly preferably used to process each commercially available conventional cultivar or the plant in use. Plant cultivars should be understood to mean plants with new characteristics ("traits") and obtained by conventional breeding, mutagenesis or recombinant DNA technology. They can be cultivars, variants, biotypes or genotypes.

[0409] Transgenic plants or plant cultivars (plants obtained by genetic engineering) which are preferably treated according to the invention include all plants which have inherited genetic material which imparts particularly 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 water or soil salinity levels, enhanced flowering performance, easier harvesting, accelerated maturation, higher yield, higher quality and / or higher nutritional value of the harvested product, better shelf life and / or processability of the harvested product. Other and particularly emphasized examples of such properties are the increased resistance of plants to animal and microbial pests (e.g. insects, arachnids, nematodes, mites, slugs and snails), due to toxins formed in the plants, in particular by genetic material from Bacillus thuringiensis (e.g. by genes CryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and combinations thereof); in addition, the increased resistance of plants to phytopathogenic fungi, bacteria and / or viruses, due to, for example, systemic acquired resistance (SAR), systemin, phytoalexins, inducers and resistance genes and correspondingly expressed proteins and toxins; and the increased tolerance of plants to certain herbicidally active compounds (e.g. imidazolinones, sulfonylureas, glyphosate or glufosinate) (e.g. "PAT" genes). In transgenic plants, the genes which impart the desired traits can also be present in combination with one another. Examples of transgenic plants which may be mentioned are important crop plants, such as cereals (wheat, rice, triticale, barley, rye, oats), corn, soybeans, potatoes, sugar beets, sugar cane, tomatoes, peas and other types of vegetables, cotton, tobacco, rapeseed and fruit plants (including fruits apples, pears, citrus fruits and grapes), with particular emphasis on corn, soybeans, wheat, rice, potatoes, cotton, sugar cane, tobacco and rapeseed. Traits that are particularly emphasized are the increased resistance of the plants to insects, arachnids, nematodes, slugs and snails.

[0410] Crop protection – treatment types

[0411] The treatment of plants and plant parts with the crystalline form A of the compound of formula (I) is carried out directly or by acting on their surroundings, habitat or storage space using conventional treatment methods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, misting, broadcasting, foaming, coating, spreading, injection, watering (wetting), drip irrigation, and in the case of propagation materials, in particular seeds, also dry seed treatment with powders, wet seed treatment with solutions, slurry treatment with water-soluble powders, treatment by encrustation, by applying one or more coatings, etc. In addition, the crystalline form A of the compound of formula (I) can also be applied by the ultra-low volume method, or the application form of the crystalline form A of the compound of formula (I) or the crystalline form A of the compound of formula (I) itself can be injected into the soil.

[0412] The preferred direct treatment of plants is foliar application, ie application of the crystalline form A of the compound of formula (I) to the leaves, wherein the frequency of treatment and the application rate should be adjusted according to the degree of infestation by the pests.

[0413] For systemic active compounds, the crystalline form A of the compound of formula (I) also enters the plant via the root system. The plant is then treated by allowing the crystalline form A of the compound of formula (I) to act on the habitat of the plant. For example, this can be achieved by soaking, for example; or mixing into the soil or nutrient solution, i.e., impregnating the location of the plant (e.g., soil or hydroponic system) with the crystalline form A of the compound of formula (I) in liquid form; or soil application, i.e., introducing the crystalline form A of the compound of formula (I) of the present invention in solid form (e.g., in the form of granules) to the location of the plant; or drip irrigation application (also commonly referred to as "chemical irrigation"), i.e., applying the crystalline form A of the compound of formula (I) of the present invention and different amounts of water from the surface or shallow surface drip line liquid at a defined location near the plant for a certain period of time. For rice crops, this can also be achieved by metering the crystalline form A of the compound of formula (I) in a solid application form (e.g., as granules) into an irrigated rice field.

[0414] Seed treatment

[0415] The method for preventing and treating animal pests by processing plant seeds has long been known, and is the theme of continuous improvement. However, there is a series of problems that cannot be solved in a satisfactory manner in the processing of seeds. Therefore, it is desirable to develop a method for protecting seeds and germinating plants, which saves or at least significantly reduces the additional application of agricultural chemicals during storage, after sowing or after plant emergence. In addition, it is desirable to optimize the consumption of active compound, so that best protection is provided for seeds and germinating plants, so that they are protected from the invasion and attack of animal pests, but the plant itself will not be damaged because of the active compound used. Especially, the method for processing seeds should also consider the inherent insecticide or nematicide characteristics of the transgenic plants with pest resistance or pest tolerance, so that the best protection of seeds and germinating plants is realized with the agricultural chemicals of minimum consumption.

[0416] Therefore, the present invention also particularly relates to a method for protecting seeds and germinating plants from pests by treating the seeds with the crystalline form A of the compound of formula (I). The method of protecting seeds and germinating plants from pests of the present invention also includes a method in which the seeds are treated with the crystalline form A of the compound of formula (I) and the mixed components simultaneously or sequentially in one operation. It also includes a method in which the seeds are treated with the crystalline form A of the compound of formula (I) and the mixed components at different times.

[0417] The invention likewise relates to the use of crystalline modification A of the compound of the formula (I) for treating seed for protecting the seed and the plants grown therefrom from attack by animal pests.

[0418] In addition, the present invention relates to seeds treated with the crystalline form A of the compound of formula (I) of the present invention to provide protection from animal pests. The present invention also relates to seeds treated simultaneously with the crystalline form A of the compound of formula (I) and mixed components. The present invention also relates to seeds treated at different times with the crystalline form A of the compound of formula (I) and mixed components. For seeds treated at different time points with the crystalline form A of the compound of formula (I) and mixed components, each substance can be present on the seeds in different layers. Herein, the layers comprising the crystalline form A of the compound of formula (I) and mixed components may optionally be separated by intermediate layers. The present invention also relates to seeds, wherein the crystalline form A of the compound of formula (I) and mixed components have been applied as components of a coating or as another layer or layers in addition to the coating.

[0419] Furthermore, the present invention relates to seeds which, after being treated with the crystalline form A of the compound of formula (I), are subjected to a film-coating process to prevent dust from abrading the seeds.

[0420] One of the advantages obtained by the crystalline form A of the compound of formula (I) with systemic action is the fact that by treating the seeds, not only the seeds themselves but also the plants grown therefrom are protected from attack by animal pests after emergence. In this way, the immediate treatment of the crop at the time of sowing or shortly after sowing can be omitted.

[0421] Another advantage that must be taken into account is that by treating the seeds with crystalline modification A of the compound of formula (I), the germination and emergence of the treated seeds can be enhanced.

[0422] It is likewise considered to be advantageous that the crystalline modification A of the compound of the formula (I) can also be used in particular for transgenic seeds.

[0423] Furthermore, the crystalline form A of the compound of formula (I) can be used in combination with compositions or compounds of signaling technology to allow for better colonization of symbionts (e.g., rhizobia, mycorrhizae and / or endophytic bacteria or fungi), and / or to optimize nitrogen fixation.

[0424] The crystalline form A of the compound of formula (I) is suitable for protecting the seeds of any plant variety used in agriculture, greenhouse, forestry or gardening. In particular, it adopts the seeds of plants in the following form: cereals (such as wheat, barley, rye, millet and oats), corn, cotton, soybean, rice, potato, sunflower, coffee, tobacco, rape, rape, beet (such as sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, kidney bean, cruciferous vegetables, onion and lettuce), fruit plants, lawns and ornamental plants. It is particularly important to process the seeds of cereals (such as wheat, barley, rye and oats), corn, soybean, cotton, rape, rape, vegetables and rice.

[0425] As mentioned above, it is also particularly important to treat transgenic seeds with the crystalline form A of the compound of formula (I). It takes the form of plant seeds that usually contain at least one heterologous gene, which controls the expression of a polypeptide having, in particular, insecticidal and / or nematicidal properties. The heterologous gene in the transgenic seeds may be derived from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. The present invention is particularly suitable for treating transgenic seeds containing at least one heterologous gene derived from Bacillus. Particularly preferred are heterologous genes derived from Bacillus thuringiensis.

[0426] In the context of the present invention, the crystalline form A of the compound of formula (I) is applied to seeds. Preferably, the seeds are treated in a sufficiently stable state to avoid being damaged during the treatment process. Generally, seeds can be treated at any time point between harvesting and sowing. The seeds usually used have been separated from the plant and the cobs, shells, stems, pods, hairs or pulp have been removed. For example, seeds that have been harvested, cleaned and dried to a moisture content that allows storage can be used. Alternatively, seeds that have been treated with water and then dried again (e.g., priming) after drying can also be used. For rice seeds, soaked seeds can also be used, for example, soaked in water to a certain stage of the rice embryo ("endosperm stage" (pigeon breast stage)), to stimulate germination and more uniform emergence.

[0427] The seed dressing formulations which can be used according to the invention can be used directly or after prior dilution with water to treat a wide variety of seed types. For example, the concentrates or the preparations obtained therefrom by dilution with water can be used for seed dressing of cereals, such as wheat, barley, rye, oats and triticale, as well as of corn, rice, rape, peas, beans, cotton, sunflower, soybeans and beets, or of various vegetable seeds. The seed dressing formulations which can be used according to the invention or their diluted use forms can also be used for seed dressing of transgenic plant seeds.

[0428] For treating the seed with the seed dressing formulations which can be used according to the invention or with the use forms prepared therefrom by adding water, all mixing apparatus which can conventionally be used for seed dressing are useful. In particular, the seed dressing process consists in placing the seed in the mixture (batchwise or continuously), adding the specific desired amount of the seed dressing formulation (as such or diluted with water beforehand), and mixing the substances used until the formulation is evenly distributed on the seed and the excess water has evaporated.

[0429] The application rate of the seed dressing formulations that can be used according to the invention can vary within a relatively wide range. The application rate is determined by the specific content of the crystalline form A of the compound of formula (I) in the formulation and the seed. The application rate is generally 0.001 to 50 g / kg seed, preferably 0.01 to 15 g / kg seed.

[0430] Table 8 Materials used in the examples

[0431] Dispersants

[0432]

[0433]

[0434] Rheological agent

[0435] Product Name CAS Number Manufacturer / Supplier Chemical name Rhodopol 23 11138-66-2 Solvay Xanthan gum AEROSIL R 972 68611-44-9 Evonik Hydrophobic modified synthetic silica

[0436] pH buffer / antifoam / biocide / antifreeze / antioxidant

[0437]

[0438] Tests and Methods Used in the Examples

[0439] method

[0440] Unless otherwise stated, all data forming part of this application have been prepared according to the methods described hereinafter. The samples for the measurements were used directly and without any further sample preparation.

[0441] XRPD

[0442] X-ray diffraction patterns were obtained using X`Pert PRO (PANalytical) and STOE STADI-P (radiation CuKα1, wavelength ) were recorded at room temperature. All X-ray reflections are in ° (θ) values ​​(peak maximum) were recorded with a resolution of ±0.2°.

[0443] Raman

[0444] Raman spectra were recorded at room temperature using a FT-Raman spectrophotometer from Bruker (models RFS100 and MultiRam). The resolution was 2 cm -1 The measurements are carried out in glass bottles or aluminium pans.

[0445] IR

[0446] IR-ATR spectra were recorded at room temperature using a FT-IR spectrophotometer Tensor 37 with a universal diamond ATR device from Bruker or a Lumos with an ATR device. The resolution was 2 cm -1 .

[0447] DSC

[0448] 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 using a perforated aluminum pan at 20 Kmin -1 or 2Kmin -1 The heating rate was 2.5 %. The flowing gas was nitrogen.

[0449] Example

[0450] I Polymorphic Form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

[0451] I.1 Preparation of polymorphic form A

[0452] Example 1

[0453] 430 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in polymorphic form B prepared as described in WO-A-2011 / 051151 was dissolved in 60 mL of toluene and the solution was filtered. One quarter of the solution was stored at room temperature and ambient humidity until the solvent evaporated. The residue was tested by thermal analysis and corresponded to the title compound in polymorphic form A.

[0454] Example 2

[0455] 404 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in polymorphic form B prepared as described in WO-A-2011 / 051151 was dissolved in 60 mL of methanol and the solution was filtered. One quarter of the solution was stored in a refrigerator until the solvent evaporated. The residue was tested by thermal analysis and corresponded to the title compound in polymorphic form A.

[0456] Example 3

[0457] 405 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one prepared as described in WO-A-2011 / 051151 in polymorphic form B was dissolved in 20 mL of ethyl acetate and the solution was filtered. 5 mL of n-heptane was added to one quarter of the solution and stored at room temperature and ambient humidity until the solvent evaporated. The residue was tested by X-ray diffraction and corresponded to the title compound in polymorphic form A.

[0458] Example 4

[0459] 413 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one prepared as described in WO-A-2011 / 051151 in polymorphic form B was dissolved in 60 mL of isopropanol and the solution was filtered. One quarter of the solution was stored at room temperature and ambient humidity until the solvent evaporated. The residue was viscous. It was scraped out and placed under room temperature and ambient conditions until it crystallized. The residue was tested by X-ray diffraction and corresponds to the title compound in polymorphic form A.

[0460] Example 5

[0461] 106 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in polymorphic form B prepared as described in WO-A-2011 / 051151 was suspended in 1 mL of water and shaken in an Eppendorf Thermomix at 25° C. (1400 rpm, shaking 30 min / stop 30 min). After one week, the suspension was dried at room temperature and ambient humidity. The residue was tested by IR spectroscopy and corresponded to the title compound in polymorphic form A.

[0462] II Polymorphic Form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one

[0463] II.1 Preparation of polymorphic form B

[0464] 4-[(6-Chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one was prepared in polymorphic Form B as described in Preparation Example 3 of WO-A-2011 / 051151.

[0465] III. Water Solubility of Flupyralidone Polymorphs

[0466] The water solubility of FPF polymorphs A and B was determined by saturating a certain amount of deionized water with the corresponding polymorph, stirring the resulting saturated suspension overnight, filtering the undissolved solid residue, and measuring the dissolved concentration of FPF in the filtrate.

[0467] Table 9: Measured water solubility of FPF polymorphs

[0468] Polymorph Polymorph composition Water solubility (g / L) A 88%A : 12%B 2.0 B 0%A: 100%B 3.2

[0469] IV Flupyralidone FS 480 Formulation Example

[0470] IV.1 Preparation of Fluopyrazone FS 480

[0471] The formulation components are weighed, homogenized with a high shear device (eg Ultraturrax or colloid mill) and subsequently ground in a bead mill (eg Dispermat SL50, 80% filling, 1.0-1.25 mm glass beads or zirconium oxide beads, 4000 rpm, recirculation milling) until a particle size of <10 μm is obtained.

[0472] Alternatively, the formulation components are mixed in a bottle and then about 25% by volume of 1.0-1.25 mm glass beads are added. The bottle is then closed, clamped in a stirring device (e.g. Retsch MM301) and processed at 30 Hz for several minutes until a particle size of <10 μm is obtained.

[0473] After grinding to the desired particle size distribution, 0.16% by weight of a thickener (e.g. xanthan gum), a biocide, a defoamer and water are added to obtain a fine suspension of the active substance. A certain amount of water is added to make the total amount 100% by weight. Diluting with water gives a stable suspension of the active substance.

[0474] Table 10: Composition of Flupyralidone FS 480

[0475]

[0476]

[0477] IV.2 Control of the fluoropyrafuranone crystal form during grinding

[0478] Table 11: Fluoropyranone crystal forms according to the grinding conditions of Fluoropyranone FS 480

[0479] FPF polymorph composition before grinding Bead Type Grinding outlet temperature FPF polymorph composition after grinding 0% Type A: 100% Type B zirconium 20-40℃ 90% Type A: 10% Type B 15% Type A: 85% Type B Glass 21-22℃ 10% Type A: 90% Type B

[0480] IV.3 Method for determining the stability of different polymorphs of flupyralidone in FS 480

[0481] Storage stability Tests were performed for a given number of weeks (w) at different temperatures (e.g. 0°C, 20°C, 30°C, 40°C, 54°C) or under thaw-freeze cycles (=TW; constant temperature change from -15°C to +30°C and back within one week).

[0482] Directly after storage Phase separation Recorded as sediment fraction and calculated as the quotient of H1 [height of the interface layer between the sediment phase and the supernatant] divided by H0 [total fill height of the sample], or in the present case recorded as supernatant fraction:

[0483] Sediment fraction = (H1 / H0)*100[%], or supernatant fraction = 100-sediment content [%]

[0484] A stable and convenient formulation is expected to have little or no phase separation during long-term storage at elevated temperatures and to be easily rehomogenized. Significant phase separation after short-term storage indicates limited storage stability and a pronounced tendency to form sediments that are difficult, if any, to disperse during storage.

[0485] Sometimes catastrophic loss of stability manifests itself as solidification of the formulation, rendering the formulation unusable.

[0486] Table 12: Stability of Flupyralidone FS 480 with Crystalline Form B

[0487]

[0488] Table 13: Stability of Flupyralidone FS 480 with Crystalline Form A

[0489]

[0490] Comments on Tables 12 and 13

[0491] As can be seen from the data in Tables 12 and 13, samples containing a certain amount of flupyrazone Form B after grinding (90% or more) were unstable during high temperature storage and completely solidified, making the formulation unusable.

[0492] The mixture of Form A and Form B of flupyralidone can be converted into Form A alone or mostly Form A during the grinding process, and then these preparations containing only or a large amount of Form A of flupyralidone can be stably stored at 40°C for 4 weeks, and some can even be stably stored at 54°C for 4 weeks.

[0493] In other words, dispersion formulations consisting mainly of the crystalline form A of flupyralidone have surprisingly better storage stability because they are suitable for high temperature storage conditions, a property that makes these formulations more reliable and practical.

[0494] Biological Test of Fluoropyrrolone (FPS) FS 480

[0495] Physicochemical properties are key drivers of systemic plant uptake and bioactivity. To test the efficacy of different FPF variants against Rhopalosiphum padi, sufficient quantities of barley seeds (variety "Scarlett", 1000-grain weight: 43.6 g) were manually coated with a dose of Flupyralidone FS 480 formulated with 100% Form A, 100% Form B, and a combination of 99% Form A and 1% Form B. The tested concentrations were 0.15 g a.i. / kg seed (commercial dose rate for cereals) and 0.075 g a.i. / kg seed. 5900g of sandy loam (75.1% sand, 10.3% clay, 14.8% silt, 1.75% humus, pH 6.9) was contained in the longitudinal boxes, and 15 seeds were sown in each box, with a spacing of about 2.5cm and a depth of 3cm. After sowing, the boxes were watered to 50-70% of the field capacity and covered with plastic film until the first plants grew out. Aphid infestation was carried out at the two-leaf stage by adding multiple pieces of infected leaf material to each test box. On the third day after the first infestation, the second reinfestation was carried out using the aforementioned method. On the 3rd and 7th days after the initial infestation, the bioactivity of the tested FPF variants was evaluated by visually evaluating the colonized leaf area and comparing it with the untreated and infested control groups. The results are expressed in terms of efficacy in percentage. 100% efficacy means that aphids cannot establish a population, and 0% means that aphids have colonized a leaf area comparable to the untreated infested control group. The growth conditions were a constant temperature of 20°C, 50% relative humidity, and a sodium pressure lamp for 14 hours. Each treatment in the experiment included 3 replicates. The results are shown in Table 14.

[0496] Table 14: Systemic biological efficacy of FPF FS 480 formulated with FPF Form A and Form B (Test Report SGRS040)

[0497]

[0498] Comments on Table 14

[0499] The tested FPF concentrations showed excellent efficacy against R. padi after seed treatment. Especially in the first evaluation, no differences were observed between the half dose rate (0.075 g / kg) and the full dose rate (0.15 g / kg). However, as expected, 0.15 g / kg produced higher residual activity. Interestingly, no differences in biological activity were observed between the various FPF variants. This result is surprising because the systemic biological efficacy of chemical active ingredients is closely related to their water solubility. The results of this experiment clearly show that the 60% reduced water solubility of FPF Form A compared to FPF Form B does not cause a reduction in biological efficacy. This, coupled with the fact that Form A is also more stable as a FS formulation, makes this form particularly convenient to use.

Claims

1. An agrochemical formulation comprising the crystalline form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of formula (1), Its X-ray powder diffraction pattern at 25°C and Cu-Kα1 radiation shows at least 3 of the following characteristic reflections recorded at 2θ values ​​±0.2°: 15.0, 20.1, 21.0, 22.4, 29.4, 33.1 and 33.2, At least 85% by weight of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one of the formula (1) is present in its crystalline form A.

2. The 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. The agricultural chemical formulation according to claim 1 or 2, comprising a) polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, b) one or more dispersants, c) one or more rheology control agents (rheology modifiers), and h) Make up to 1 L (liter) of carrier (filler).

4. The agricultural chemical formulation according to claim 1 or 2, comprising a) polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, b) one or more dispersants, c) one or more rheology control agents (rheology modifiers), d) one or more pH buffers, e) one or more defoaming agents, f) one or more biocides, g) one or more antifreeze agents, and h) Make up to 1 L (liter) of carrier (filler).

5. The agricultural chemical formulation according to claim 3, comprising a) The concentration range is 400-500g / L, b) The concentration range is 60-80g / L, c) concentration range of 6-10 g / L, and h) Make up to 1L of water.

6. The agricultural chemical formulation according to claim 4, comprising a) The concentration range is 400-500g / L, b) The concentration range is 60-80g / L, c) The concentration range is 6-10g / L, d) The concentration range is 0.01-10g / L, e) The concentration range is 0.1-2g / L, f) The concentration range is 0.1-3g / L, g) concentration range is 10-100 g / L, and h) Make up to 1L (liter) of water.

7. Agrochemical formulation according to one or more of the preceding claims, comprising as component i) one or more further adjuvants and auxiliaries.

8. Agrochemical preparation according to one or more of the preceding claims, comprising one or more further active ingredients k).

9. Agrochemical preparation according to one or more of the preceding claims for use as seed coating.

10. A process for preparing the crystalline form [A] of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, the process comprising the steps of: a) diluting and / or suspending the compound of formula (1) in a suitable solvent or solvent mixture; b) adjusting the temperature to 0 to 25°C; and c) storing the solution or slurry obtained in step b) at a temperature of 0 to 25° C., Until the solvent evaporates and crystals of polymorph Form A are formed.

11. The method according to claim 10, wherein the solvent is selected from toluene, methanol, ethanol, butanol, ethyl acetate, isopropanol or water.

12. The method according to claim 10, wherein the solvent is selected from toluene, methanol, ethanol, butanol, ethyl acetate, isopropanol or water.

13. A process for preparing the crystalline form [A] of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one by grinding the crystalline form [B] or a mixture of [A] and [B] in a bead mill with glass beads or zirconium oxide beads.

14. Form A of the compound according to claim 1, which has an X-ray powder diffraction pattern at 25°C and using Cu-Kα1 radiation showing at least the following characteristic reflections recorded at 2θ values ​​±0.2°: 15.0, 20.1, 21.0, 22.4 and 29.

4.

15. Form A of the compound according to claim 1, which has an X-ray powder diffraction pattern at 25°C and using Cu-Kα1 radiation showing at least the following characteristic reflections recorded at 2θ values ​​±0.2°: 15.0, 20.1, 21.0, 22.4, 29.4, 33.1 and 33.2, and Its Raman spectrum shows at least the following bands (in cm -1 peak maximum values): 111, 880 and 1711, and Its IR spectrum shows at least the following bands (in cm -1 Peak maxima calculated): 809, 1071 and 1597.

16. Use of the polymorphic form [A] according to claim 13 for the preparation of an agrochemical formulation with improved storage stability.

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