EA044988B1 - CRYSTAL FORMS OF 1-(1,2-DIMETHYLPROPYL)-N-ETHYL-5-METHYL-N-PYRIDAZIN-4-YL-PYRAZOL-4-CARBOXAMIDE - Google Patents

Description

The present invention relates to a new crystalline form of 1-(1,2-dimethylpropyl)-N-ethyl5-methyl-K-pyridazin-4-yl-pyrazol-4-carboxamide, recently given the common name dimpropyridase.

The invention also relates to the use of crystalline Form B for the control of invertebrate pests and to plant protection compositions which contain crystalline Form B 1-(1,2dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole -4-carboxamide.

-(1,2-Dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide is a pesticide active substance of formula I, which has a center of chirality and can thus be present in in the racemic form depicted in formula (I), as well as in the form of its enantiomers of formulas I-R and I-S or in the form of non-racemic mixtures thereof (see ip.com IPCOM000256756D).

(I)

(I-R) (I-S)

-(1,2-Dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide, its activity against arthropod pests and general procedures for its preparation are known from WO 2012/143317. Application of these general procedures to the preparation of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4yl-pyrazol-4-carboxamide gives this compound as a glassy melt which contains the crystalline Form A described below.

For the production of active substances on an industrial scale, as well as for the formulation of active substances, in many cases knowledge of the possible existence of crystalline modifications, also described as crystalline forms or polymorphs, or solvates (pseudopolymorphs) of the corresponding active substance, as well as knowledge of specific properties of such modifications and solvates and methods for their preparation. A number of active substances can exist in various crystalline as well as amorphous modifications. In these cases, the term polymorphism is used. A polymorph is a solid crystalline phase of a compound, which is characterized by a specific uniform packing and arrangement of molecules in the solid.

Different modifications of the same active substance may sometimes have different properties, for example differences in the following properties: solubility, vapor pressure, dissolution rate, resistance to phase change to another modification, stability during grinding, suspension stability, optical and mechanical properties, hygroscopicity, crystal shape and size, filterability, density, melting point, resistance to decomposition, color and sometimes even chemical reactivity or biological activity.

The applicant's own attempts to isolate 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4yl-pyrazol-4-carboxamide into a crystalline solid by crystallization initially resulted in a crystalline material which was difficult to handle handle, and whose resistance to uncontrolled phase transition was unsatisfactory. This modification is also described below as Form A. This instability of suspensions of crystalline Form A to uncontrolled phase transition may adversely affect the preparation of 1-(1,2-dimethylpropyl)-N-ethyl-5methyl-N-pyridazin-4-yl-pyrazole formulations -4-carboxamide. This instability of crystalline Form A to uncontrolled phase transition may also impair the stability of Form A pesticide formulations or its ability to form substantially homogeneous aqueous solutions. This is because uncontrolled particle growth due to phase change may occur during production, storage or dilution.

Currently, a previously unknown stable crystalline form of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide has been unexpectedly discovered. This new crystalline form can be obtained in high purity by suitable methods. This crystalline form is also described below as crystalline form B or polymorph B, respectively. At least at room temperature, this crystal form B is thermodynamically more stable than crystal form A. In particular, crystal form B does not exhibit the disadvantages of crystal form A.

Accordingly, the first aspect of the present invention relates to crystalline Form B of 1(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide as described in the present invention.

Another object of the present invention is solid 1-(1,2-dimethylpropyl)-N- 1 044988 ethyl-5-methyl-K-pyridazin-4-yl-pyrazol-4-carboxamide, which consists of at least 90 wt. % in particular, at least 95% of crystalline Form B relative to the 1-(1,2-dimethylpropyl)-Cethyl-5-methyl-K-pyridazin-4-yl-pyrazol-4-carboxamide contained in the solid.

The present invention also relates to a plant protection composition containing crystalline Form B of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-M-pyridazin-4-yl-pyrazol-4-carboxamide, as defined herein the invention and one or more carriers customary for the preparation of plant protection compositions.

The present invention particularly relates to a plant protection composition containing 1(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide and one or more carriers conventional for preparing compositions for plant protection, wherein the 1-(1,2-dimethylpropyl)K-ethyl-5-methyl-K-pyridazin-4-yl-pyrazol-4-carboxamide contained in the composition is essentially in crystalline form B, that is, the 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4carboxamide contained in the composition consists of at least 90% by weight, in particular at least at least 95 wt.% from crystalline Form B, as defined in the present invention.

The invention also relates to the following objects:

use of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-ylpyrazol-4-carboxamide crystalline Form B as defined in the present invention or a plant protection composition as defined in the present invention for control or suppression of invertebrate pests;

use of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-ylpyrazol-4-carboxamide crystalline Form B as defined herein or a plant protection composition as defined herein for protecting crops, plants or plant propagation material from attack or infestation by invertebrate pests;

a method of controlling or suppressing invertebrate pests, comprising contacting said pest or its food resources, or its habitat or breeding site with crystalline form B 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl- K-pyridazin-4-yl-pyrazol-4carboxamide, as defined in the present invention; and a method of protecting crops, plants or plant propagation material from attack or infestation by invertebrate pests, comprising contacting said crops, growing plants or plant propagation material, or soil or water in which the plant is growing, with crystalline form B 1-(1,2-dimethylpropyl)-Cethyl-5-methyl-K-pyridazin-4-yl-pyrazol-4-carboxamide, as defined in the present invention.

As a consequence of its thermodynamic stability, crystalline Form B according to the present invention is easier to handle than the previously known crystalline Form A 1-(1,2dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol- 4-carboxamide. During production, Crystal Form B is obtained as discrete crystals or crystallites that do not suffer from uncontrolled phase transition and consequent increase in particle size. In particular, crystalline Form B formulations, and especially pure crystalline Form B formulations, exhibit increased stability against conversion to another solid form and therefore increased stability against increasing particle size and resulting instability of the formulation or solution. In particular, the stability of the formulation, which contains 1-(1,2-dimethylpropyl)-C-ethyl-5methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide, essentially in the form of crystalline Form B, is noticeably higher than stability of the composition, which contains crystalline form A of 1-(1,2-dimethylpropyl)C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide.

Here and throughout the specification, the terms Form B, Modification B, Polymorph B and Crystal Form B are used interchangeably and refer to Crystal Form B 1-(1,2-dimethylpropyl)-Cethyl-5-methyl-K-pyridazin-4-yl -pyrazole-4-carboxamide, as defined in the present invention. Likewise, the terms form A, modification A, polymorph A and crystalline form A are used interchangeably and refer to crystalline form A of 1-(1,2-dimethylpropyl)-C-ethyl-5methyl-C-pyridazin-4-yl-pyrazole -4-carboxamide, as defined in the present invention.

The terms pure form B, pure polymorph B and pure crystalline form B should be understood to mean that the proportion of polymorph B in the solid form is 1-(1,2-dimethylpropyl)-C-ethyl-5-methylK-pyridazin-4-yl-pyrazole -4-carboxamide constitutes at least 90% by weight and in particular at least 95% by weight, based on the total amount of 1-(1,2-dimethylpronyl)-N-ethyl-5-methyl-Npyridazin-4 -yl-pyrazol-4-carboxamide present in the solid. In other words, pure Form B means that the solid form of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-ylpyrazol-4-carboxamide does not contain more than 10% by weight and especially not more than 5% by weight of any solid form other than polymorph B, based on the total amount of 1-(1,2-dimethylpropyl)-C-ethyl-5methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide, present in the solid.

Polymorph B according to the present invention can be identified by X-ray powder diffractometry based on its X-ray powder diffraction pattern, hereinafter also referred to as powder X-ray diffraction pattern or PRD pattern, of polymorph Form B recorded using Cu-Ka radiation (1.54178 A) at

- 2 044988

25°C displays the following 3 reflections, indicated as 2θ values: 20.69±0.10°, 24.15±0.10° and 30.52±0.10°. In addition to these 3 reflections, polymorph B according to the present invention may display one or more, in particular at least 2, often at least 4, in particular at least 6 or at least 8 reflections in such a PDR pattern and in particular all of the reflections given below as 2θ values: 7.99±0.10°, 10.07±0.10°, 12.38±0.10°, 15.31±0.10°, 15.97±0.10°, 16.50±0.10°, 18.03±0.10°, 19.29± 0.10°, 20.22±0.10°, 20.96±0.10°, 23.40±0.10°, 23.70±0.10°, 26.09±0.10°, 27.26±0.10° and 32.91±0.10°.

Of these reflections, preferably at least 1, in particular at least 2, more preferably at least 4, in particular at least 6 or all of the following reflections, indicated as 2θ values, can be observed in such a PDR picture: 10.07 ±0.10°, 15.31±0.10°, 15.97±0.10°, 16.50±0.10°, 19.29±0.10°, 20.22±0.10°, 20.96±0.10° and 26.09±0.10°. In addition to these reflections, preferably at least 1, in particular at least 2, more preferably at least 4, in particular at least 6 or all of the following reflections, indicated as 2θ values, can be observed in such a PDR pattern: 7.99±0.10°, 12.38±0.10°, 18.03±0.10°, 23.40±0.10°, 23.70±0.10°, 27.26±0.10° and 32.91±0.10°.

Often the PXR pattern of polymorph Form B recorded using Cu-Ka radiation (1.54178 A) at 25°C displays the following 3 reflections, indicated as 20θ values: 20.69±0.10°, 24.15±0.10° and 30.52±0.10° and additionally the following reflections reported as 2θ values: 15.31±0.10°, 15.97±0.10° and 16.50±0.10°.

As an alternative to the PRD, the pattern of polymorph Form B recorded using Cu-Ka radiation (1.54178 A) at 25°C displays the following 3 reflections, reported as 2θ values: 20.69±0.10°, 24.15±0.10° and 30.52±0.10° and additionally the following reflections are given as 2θ values: 23.40±0.10° and 23.70±0.10°.

In particular, the PXR pattern of polymorphic form B recorded using Cu-Ka radiation (1.54178 A) at 25°C displays the following 3 reflections, indicated as 2θ values: 20.69±0.10°, 24.15±0.10° and 30.52±0.10° and additionally the following reflections are reported as 2θ values: 15.31±0.10°, 15.97±0.10°, 16.50±0.10°, 23.40±0.10° and 23.70±0.10°.

X-ray studies at 100 K on a single crystal of polymorph B demonstrate that the main crystal structure is monoclinic. The unit cell has the space group Ρ2μ. The structural resolution of the X-ray diffraction data of single crystals obtained in this way showed that the unit cell contains 2 molecules of 1-(1,2-dimethylpropyl)-C-ethyl-5methyl-C-pyridazin-4-yl-pyrazol-4- carboxamide, not a solvent molecule. The asymmetric unit of the crystal structure contains one molecule of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-Npyridazin-4-yl-pyrazol-4-carboxamide. Although the X-ray diffraction pattern calculated from single-crystal X-ray diffraction data obtained at 100 K differs from the powder X-ray diffraction pattern experimentally determined at 25°C, good agreement between the calculated and measured XRD patterns can be achieved by adjusting the unit cell dimensions to PRD data.

Characteristic data of the crystal structure of polymorph B, determined at 100 K, are presented in the following table. 1. In addition, values calculated from powder X-ray reflectance data obtained at 25°C are given.

- 3 044988

Table 1

Crystallographic characteristics of polymorph B

Options Polymorph B Single crystal data Powder X-ray data Class monoclinic monoclinic Space group Р2г P2fn a (A) 11.1315(5) 11.35(2) b (A) 6.7075(3) 6.76(1) C (A) 11.1987(5) 11.29(1) A 90° 90° β 102.2190(10)° 11.29(1) γ 90° 90° ζ 2 2 Wavelength 1.54178 A 1.54178 A Temperature 100 K 298 K Calculated data Volume (A ⁵ ) 817.20(6) density (g/m ³ ) 1.225 R factor (%) 6.73

a, b, c = unit cell length, α, β, γ = unit cell angle,

Z = number of molecules in a unit cell.

When analyzed by differential scanning calorimetry (DSC), Form B in accordance with the present invention displays a thermogram with a characteristic endothermic peak, also called a melting peak. The melting point, defined as the onset of peak melting, is typically in the range of about 80 to 90°C, particularly in the range of 82 to 89°C. The values given here refer to those determined by DSC using an aluminum closed cup with a sample size of 1 - 10 mg and a heating rate of 10 K/min.

Thermogravimetric analysis, also referred to as TGA, showed that there was no mass loss upon heating, which confirmed the results of single crystal X-ray diffraction studies that Form B was solvent-free.

The solid-state ^13C NMR spectrum of Form B shows the following resonance peaks relative to standard tetramethylsilane (TMS, 1% in CDC^): 165.3±0.3, 152.7±0.3, 149.9±0.3, 141.9±0.3, 141.1±0.3, 119.7±0.3, 118.9± 0.3, 113.8±0.3, 61.2±0.3, 60.4±0.3, 39.8±0.3, 32.9±0.3, 31.9±0.3, 21.4±0.3, 19.4±0.3, 17.9±0.3, 16.3±0.3, 12.8±0.3, 9.4±0 .3 and 9.0±0.3 part. per million. The pairs of resonance peaks shown in the following table show significant overlap with the centers also shown in the table. 2:

table 2

Peak pair [frequency, per million] Peak center [frequency, per million] 141.9+0.3; 141.1+0.3 141.5+0.9 119.7+0.3; 118.9+0. 119.3+0.9 61.2+0.3; 60.4+0.3 60.8+0.9 32.9+0.3; 31.9+0.3 32.4+0.9 9.4+0.3; 9.0+0.3 9.2+0.9

The resonance peaks reported in the present invention were obtained by recording solid-state ¹³ C NMR spectra at 25° C. (purge gas temperature) and 14.1 tesla at magic angle rotation at 10 kHz. Semi-quantitative solid-state ¹³ C NMR spectra recorded with 1H- ¹³ C cross-polarization and quantitative solid-state ¹³ C NMR spectra recorded with direct ¹³ C polarization show the same positions of resonance peaks within the 031 part. per million. The resonance peak positions shown here are the average of the positions measured in the semiquantitative spectrum and the quantitative spectrum. Semi-quantitative solid-state ¹³ C NMR spectra were recorded at 25°C and 14.1 tesla at magic angle spinning at 10 kHz spin speed with 3 ms ¹ H ^-13 C cross-polarization and 2 s rescan delay. Quantitative solid-state ¹³ C NMR spectra were recorded with direct ¹³ C polarization, such as 5 μs 90° forward pulse polarization and 1H heteronuclear dipolar decoupling, with a rescan delay of 300 s.

The shape and relative intensity of the quantitative spectrum of solid-state ¹³ C NMR are characteristic of form B in that the integral of the resonance peak at 19.4 parts. per million is 25.9%±2.0%, in

- 4 044988 in particular, 25.9%±1.4% and in particular 25.9%±1.0% with respect to the total integral of the resonant peaks in the range from 20.4 to 18.6 parts. per million

Form B of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide according to the invention can be obtained by crystallization from solutions of 1-(1,2-dimethylpropyl )-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide or in ethyl acetate; or a mixture of n-butyl acetate and n-heptane, preferably in a volume ratio of n-butyl acetate to nheptane in the range from 1: 1 to 1: 4; or a mixture of toluene and cyclohexane, preferably in a volume ratio of toluene to cyclohexane in the range of 1: 2 to 1: 6.

Crystallization of Form B from its solution is preferably carried out under controlled conditions, i.e. The crystallization conditions are chosen to achieve a slow crystallization rate. In particular, crystallization of Form B is accomplished by controlled cooling of a hot solution of 1-(1,2dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide in one of the above mentioned solvents or solvent mixtures.

To do this, in the first stage I) a hot solution of 1-(1,2-dimethylpropyl)-Cethyl-5-methyl-K-pyridazin-4-yl-pyrazol-4-carboxamide can be prepared in one of the above organic solvents or a mixture of solvents , and then in the second stage II) crystallization of 1-(1,2dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide is carried out by controlled cooling.

The temperature of the hot solution is usually at least 50°C and in particular in the range from 50 to 130°C. Naturally, the temperature of the hot solution will not exceed the boiling point of the solvent or mixture of solvents. Often the temperature of the hot solution does not exceed 100°C.

Controlled cooling means that the temperature of the solution is slowly reduced, for example by applying a cooling rate of no more than 50 K/h and in particular no more than 20 K/h. Often the hot solution is cooled using a cooling rate in the range of 1 to 50 K/h, in particular in the range of 2 to 20 K/h. During cooling, the cooling rate can be constant, but it is also possible to start with a low cooling rate and increase the cooling rate once crystallization has already begun. Likewise, cooling can be started at a high cooling rate until the temperature is close to, but above, the temperature at which the concentration of 1-(1,2dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl -pyrazole-4-carboxamide in solution corresponds to the equilibrium concentration, and then reduce the cooling rate. Preferably, crystallization starts at a temperature of no more than 100°C, in particular no more than 80°C, for example in the range from 30 to 100°C, in particular in the range from 40 to 80°C. In particular, the above cooling rates apply at least in this temperature range.

The concentration of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide in the solution used for crystallization naturally depends on the nature of the solvent and the temperature of the solution, often is in the range from 50 to 500 g/l. Suitable conditions can be determined by one skilled in the art through routine experimentation.

The solution used for crystallization is preferably substantially free of solvents other than those specified. In this context, essentially free means that the concentration of other solvents in the 1-(1,2-dimethylpropyl)-K-ethyl-5-methyl-K-pyridazin-4-yl-pyrazol4-carboxamide-containing solution does not exceed 10 wt. %, often 5 wt.%, based on the total amount of solvent.

During the crystallization process, the mixture to be crystallized, i.e. a solution of 1-(1,2-dimethylpropyl)-C-ethyl5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide and a mixture of crystalline 1-(1,2-dimethylpropyl)-Cethyl-5-methyl-K -pyridazin-4-yl-pyrazol-4-carboxamide and solvent can be mixed. However, in principle there is no need to stir the mixture.

Typically, the crystallization mixture is cooled to a temperature at which at least 80% or at least 90% of the 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-ylpyrazol-4- has crystallized. carboxamide contained in the hot solution. This temperature is often in the range from -20 to +30°C, in particular in the range from -10 to +20°C. It is possible to concentrate the crystallization mixture, for example by evaporating the solvent, to increase the yield of Form B.

In addition, the crystallization of Form B can be carried out in analogy with conventional crystallization processes for organic compounds using crystallization devices well known in the art. Likewise, separation of crystalline Form B can be accomplished by analogy with methods well known in the art, such as filtration, decantation or centrifugation.

In a specific embodiment of the invention, the 1-(1,2-dimethylpronul)-N-ethyl-5-methyl-Npyridazin-4-yl-pyrazol-4-carboxamide used to prepare Form B is at least 85% pure, often at least 90%, in particular at least 95%, i.e. the content of organic impurities that are not organic solvents is not more than 15

- 5 044988 wt.%, often not more than 10 wt.%, and in particular not more than 5 wt.%, calculated as 1-(1,2-dimethylpropyl)K-ethyl-5-methyl-K-pyridazin- 4-yl-pyrazol-4-carboxamide used for crystallization.

A solution of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide can be prepared, for example, by the following methods:

(1) dissolving 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide, preferably in a form other than Form B, in one of the above-mentioned organic solvents, or (2) preparing 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide by chemical reaction and transferring the reaction mixture if necessary after removal reagents and/or by-products, into an organic solvent suitable in accordance with the invention.

To prepare a hot solution of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-ylpyrazol-4-carboxamide, essentially any known form of 1-(1,2-dimethylpropyl) can be used. -C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide. The crystalline Form A of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4carboxamide described below will often be used, but Form B or a mixture of Form A and Form B. 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide used to prepare Form B may be racemic or enriched in one of its enantiomers . 1-(1,2dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide used to prepare the hot solution is often at least 85% pure, often at least 90 %, in particular at least 95%.

The dissolution of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide usually occurs at elevated temperatures, in particular at 50°C, especially at in the range from 50 to 130°C. Naturally, the temperature used for dissolution should not exceed the boiling point of the solvent or solvent mixture. The hot solution is then subjected to controlled cooling as described in the present invention.

A hot solution of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4carboxamide can also be prepared by transferring the reaction mixture obtained by chemical reaction, which contains 1-(1 ,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4carboxamide, if necessary after removal of reagents and/or by-products, into an organic solvent suitable in accordance with the invention. This can be carried out in such a way that the reaction is carried out in an organic solvent or solvent mixture which consists at least partly, preferably at least 50% by weight, of a solvent suitable for crystallization, and if necessary a treatment is carried out during which Excess reagents and any catalysts present are removed, as well as any unsuitable solvents, such as water from water treatment and salts formed as by-products. Preparation of a solution of 1-(1,2-dimethylpropyl)-K-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide by chemical reaction of a suitable precursor 1-(1,2-dimethylpropyl)-K- ethyl 5-methyl-K-pyridazin-4yl-pyrazol-4-carboxamide can be carried out in analogy with the methods described in the prior art cited at the beginning, which is hereby referred to in its entirety.

The method for preparing Form B provides 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-ylpyrazol-4-carboxamide in high purity. In particular, crystalline form B has a 1(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide content of at least 94% by weight, in particular at least 96%, in particular at least 98%.

As stated above, 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4carboxamide can also exist in another crystalline form A, hereinafter referred to as polymorph A. Polymorph A can be identified and distinguished from Form B by powder X-ray diffractometry. The PXR pattern of the Form A polymorph recorded using Cu-Ka radiation (1.54178 A) at 25°C shows at least 3 or all of the following reflections, reported as 2θ values: 16.16±0.10°, 20.36±0.10°, 23.92±0.10 °, 24.29±0.10° and 27.43±0.10°. These reflections are not present in form B. In addition to these 5 reflections, polymorph A may display one or more, in particular at least 2, often at least 4, in particular at least 6, or at least 8 reflections and in particular all of the reflections listed below as 2θ values: 7.95±0.10°, 10.16±0.10°, 12.40±0.10°, 15.31±0.10°, 15.89±0.10°, 16.53±0.10°, 18.02±0.10°, 19.25±0.10°, 20.93±0.10°, 23.44±0.10°, 23.70±0.10°, 26.16±0.10°, 30.71±0.10° and 32.92±0.10°.

Among the peaks of the PRD pattern of polymorphic form A, the most noticeable are the peaks at the following 2θ values: 10.16±0.10°, 15.31±0.10°, 15.89±0.10°, 16.16±0.10°, 16.53±0.10°, 19.25±0.10°, 20.36±0.10° , 20.93±0.10°, 23.44±0.10°, 23.70±0.10°, 23.92±0.10°, 224. 29±0.10°, 26.16±0.10°, 30.71±0.10° and 32.92±0.10°.

When analyzed by differential scanning calorimetry (DSC), Form A in accordance with the present invention displays a thermogram with a characteristic endothermic peak, also called a melting peak. Melting point, defined as the beginning of the melting peak,

- 6 044988 is typically in the range of about 82 to 87°C. The values given here refer to those determined by DSC using an aluminum closed cup with a sample size of 1 to 10 mg and a heating rate of 10 K/min.

Thermogravimetric analysis, also referred to as TGA, showed that there was no mass loss upon heating, indicating that Form A was solvent-free.

The solid-state ¹³ C NMR spectrum of Form A shows the following resonance peaks relative to standard tetramethylsilane (TMS, 1% in CDCl ₃ ): 165.3±0.3, 152.7±0.3, 149.9±0.3,141.9±0.3, 141.1±0.3, 119.7±0.3, 118.9± 0.3, 113.8±0.3, 61.2±0.3, 60.4±0.3, 39.8±0.3, 32.9±0.3, 31.9±0.3, 21.4±0.3, 19.4±0.3, 17.9±0.3, 16.3±0.3, 12.8±0.3, 9.4±0 .3 and 9.0±0.3 part. ppm. The resonance peaks reported in the present invention were obtained by recording both semi-quantitative and quantitative solid-state ¹³ C NMR spectra as described for Form B.

The shape and relative intensity of the quantitative spectrum of solid-state ¹³ C NMR are characteristic of form A in that the integral of the resonance peak at 19.4 parts. per million is 21.2%±2.0%, in particular 21.2%±1.4% and in particular 21.2%±1.0% with respect to the total integral of the resonant peaks in the range from 20.4 to 18.6 parts. per million

Form A can be prepared using the protocols of Examples 1 and 2, respectively, from WO 2012/143317 for the preparation of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4carboxamide Similarly. In addition, Form A is formed by evaporation of warm solutions of 1-(1,2dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide in methanol, isopropanol, dimethylformamide, pyridine, N- methylpyrrolidone or 3-methylbutan-2-one.

Like other forms of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4carboxamide known from WO 2012/143317, Form B 1-(1,2- dimethylpronyl)-N-ethyl-5-methyl-Npyridazin-4-yl-pyrazol-4-carboxamide is useful for the control or suppression of invertebrate pests, in particular arthropod pests and especially insect pests. However, it is superior to them in terms of processing properties and composition, in particular due to its excellent phase change stability.

Therefore, a further aspect of the present invention relates to the use of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide crystalline Form B for the preparation of plant protection compositions, containing solid 1-(1,2-dimethylpropyl)-N-ethyl-5-methylN-pyridazin-4-yl-pyrazol-4-carboxamide.

Thus, the invention also relates to plant protection compositions which contain crystalline form B and carriers customary for plant protection compositions, in particular plant protection compositions in the form of suspensions (for example SC, OD, FS), in particular , aqueous suspension concentrates (so-called SC or FS) or non-aqueous suspension concentrates (so-called OD), and crop protection products in the form of wettable powders or fine powders (e.g. WP, SP, WS, DP, DS), compressed products ( e.g. BR, TV, DT), granules (e.g. WG, SG, GR, FG, GG, MG), in particular those granules that are dispersed in water. Form B plant protection compositions also include gel compositions, in particular for the treatment of plant propagation material such as seeds (eg GF). These and other types of compositions are defined in the Catalog of pesticide formulation types and international coding system, Technical Mono-graph No. 2, 6th ed. May 2008, CropLife International. Form B plant protection compositions can be prepared in a known manner as described in Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

The plant protection compositions in accordance with the present invention contain Form B and one or more carriers conventional for the preparation of plant protection compositions. In particular, at least 90% of the 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide contained in such a formulation is present as Form B. In such a plant protection composition, the amount of active substance, i.e. the total amount of 1-(1,2-dimethylnponyl)-N-ethyl-5-methyl-Npyridazin-4-yl-pyrazol-4-carboxamide and other active substances, if necessary, is usually in the range from 1 to 98% by weight. in particular in the range from 2 to 95% by weight, based on the total weight of the plant protection composition.

Suitable carriers are all solid and liquid substances which are commonly used as carriers in plant protection compositions, in particular in insecticidal compositions. Liquid carriers are typically solvents and mixtures of solvents and surfactants. One skilled in the art will appreciate that for liquid formulations, the liquid carrier will be selected such that the solubility of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4yl-pyrazol-4-carboxamide in liquid phase of the formulation was significantly lower than the desired concentration of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide in the formulation.

Suitable solvents for use in liquid carriers are water and organic solvents, and mixtures thereof, wherein 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4- 7 044988 carboxamide has a solubility of no more than 40 g/l at 25°C and 1 bar. However, solvents in which the solubility of 1-(1,2-dimethylpronul)-N-ethyl-5-methyl-Npyridazin-4-yl-pyrazol-4-carboxamide is higher may also be used, provided that the solubility is 1 -(1,2dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide in the liquid phase of the composition is quite low. Suitable organic solvents for liquid carriers are, in particular, mineral oil fractions with medium to high boiling points, such as kerosene or diesel oil; oils of vegetable or animal origin; aliphatic and alicyclic hydrocarbons such as hexane, heptane and cyclohexane, and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, for example silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, for example cellulose, starch; fertilizers, for example ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of plant origin, such as cereal flour, tree bark flour, wood flour, nut shell flour and mixtures thereof.

In addition to the carrier, the compositions of the present invention may contain excipients commonly used in such compositions. Typical excipients include surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, repellents, attractants, food stimulants, compatibilizers, bactericides (preservatives), antifreezes, antifoams, dyes, tackifiers and binders, as well as viscosity modifying additives (thickeners and rheology modifiers) and pH adjusting agents such as buffers.

Suitable surfactants include surfactants such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes and mixtures thereof. Such surfactants can be used as an emulsifier, dispersant, solubilizer, wetting agent, penetration aid, protective colloid, or adjuvant. Examples of surfactants are given in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International ed. or North American ed.).

Suitable anionic surfactants are alkaline, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, fatty acid and oil sulfonates, ethoxylated alkylphenol sulfonates, alkoxylated arylphenol sulfonates, condensed naphthalene sulfonates, dodecyl and tridecylbenzene sulfonates, naphthalene and alkyl naphthalene sulfonates , sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkyl phenol ethoxylates.

Suitable nonionic surfactants include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated by 1 to 50 equivalents. For alkoxylation, ethylene oxide and/or propylene oxide, preferably ethylene oxide, can be used. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, sucrose-glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinyl alcohols or vinyl acetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups or long-chain primary amine salts. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are type A-B or A-B-A block polymers containing blocks of polyethylene oxide and polypropylene oxide or type A-B-C containing alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds which themselves have little or no pesticidal activity and which improve the biological effectiveness of the target compound. Examples are surfactants, mineral or vegetable oils and other excipients. Additional examples are listed at

Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.

The plant protection compositions according to the invention may also contain one or more viscosity modifying additives (rheology modifiers). By them, in particular, we mean substances and mixtures of substances that give the composition an altered fluidity, for example, a high viscosity at rest and a low viscosity when in motion. The nature of the rheology modifier is determined by the nature of the composition. Examples of rheology modifiers include inorganic substances such as layered silicates and organically modified layered silicates such as bentonites or attapulgites (e.g. Attaclay, Engelhardt Co.), and organic substances such as polysaccharides and heteropolysaccharides such as Xanthan Gum® ( Kelzan® from Kelco Co.), Rhodopol® 23 (Rhone Poulenc) or Veegum® (R.T. Vanderbilt Co.).

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkyl isothiazolinones and benzisothiazolinones.

Suitable antifreezes are ethylene glycol, propylene glycol, urea and glycerin.

Suitable antifoaming agents include silicones, long-chain alcohols and fatty acid salts.

Suitable dyes (eg red, blue or green) are pigments with low water solubility and water-soluble dyes. Examples are inorganic dyes (eg, iron oxide, titanium oxide, iron hexacyanoferrate) and organic dyes (eg, alizarin, azo, and phthalocyanine dyes).

Examples of antifoam agents are silicone emulsions known for this purpose (Silikon® SRE, Wacker Co. or Rhodorsil® from Rhodia Co.), long chain alcohols, fatty acids and their salts, foam suppressants such as aqueous wax dispersions, solid foam suppressants ( so-called compounds) and organofluorine compounds and mixtures thereof. The amount of antifoaming agent is usually from 0.1 to 1% by weight, based on the total weight of the plant protection agent.

Suitable tackifiers or binders are polyvinylpyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes and cellulose ethers.

If necessary, the formulations may contain one or more buffers to adjust the pH. Examples of buffers are salts of alkali metals and weak inorganic or organic acids, such as, for example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.

A preferred group of embodiments of the invention relates to liquid formulations of Form B. In addition to the solid phase of the active substance, these compositions contain at least one liquid phase in which Form B is present in the form of dispersed fine particles. As mentioned above, the liquid phase contains at least one of the above-mentioned solvents and additional auxiliary substances, provided that Form B is only slightly soluble or insoluble in it, for example that the solubility of Form B at 25° C. and 1013 mbar in the liquid phase is no more than 20 g/l.

A first preferred embodiment of the invention relates to liquid compositions in which the solvent contained in the liquid phase is selected from water and mixtures of aqueous solvents, that is, mixtures of solvents which, in addition to water, also contain one or more organic solvents miscible with water in an amount of up to 20 wt.%, however, preferably not more than 10 wt.%, based on the total amount of water and solvent contained in the liquid phase. Suitable water miscible solvents are, for example, water miscible ethers such as tetrahydrofuran, methyl glycol, methyl diglycol, alkanols such as ethanol or isopropanol, or polyols such as glycol, glycerin, diethylene glycol, propylene glycol and the like.

Formulations in which the solvent contained in the liquid phase is selected from water and mixtures of aqueous solvents can be formulated as aqueous suspension concentrates (SC) or as aqueous gels (GW, GF).

Such aqueous suspension concentrates contain Form B in the form of fine particles, with the Form B particles suspended in the aqueous liquid. The particle size of the active substance, that is, the size which does not exceed 90% by weight of the particles of the active substance, is in this case usually less than 30 μm, in particular less than 20 μm. Advantageously, in the SC according to the invention at least 40% by weight and in particular at least 60% by weight of the particles have a diameter of less than 5 μm.

In such SCs, the amount of active substance, i.e. the total amount of 1-(1,2-dimethylpropyl)-C-ethyl-5methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide and other active substances, if necessary, is usually in the range from 2 to 60% by weight. , in particular in the range from 5 to 40 wt.%, calculated

- 9 044988 for the total weight of the suspension concentrate.

In addition to the active substance, aqueous suspension concentrates usually contain surfactants and they may also contain, if necessary, one or more auxiliary substances selected from antifoams, thickeners (= rheology modifiers), antifreezes, biocides and pH adjusting agents , for example, buffers.

Possible surfactants are the previously mentioned surfactants. Preferably, the aqueous plant protection composition according to the present invention contains at least one of the previously mentioned anionic surfactants and, if necessary, one or more nonionic surfactants. The amount of surfactants is generally from 1 to 50% by weight, in particular from 2 to 30% by weight, based on the total weight of the aqueous SC according to the invention. Preferably, the surfactant includes at least one anionic surfactant and at least one nonionic surfactant, and the ratio of anionic surfactant to nonionic surfactant is typically in the range of 10:1 to 1: 10.

Regarding the nature and quantity of antifoams, thickeners, antifreezes, buffers and biocides, the same applies as above.

Aqueous gels (GW, GF) can be similar to the above-mentioned suspension concentrates. Unlike conventional suspension concentrates, aqueous gels contain a gelling agent in such an amount that the composition is no longer a runny liquid, but a thick gel. Suitable gelling agents are, for example, carboxymethylcellulose and superabsorbent polymers.

According to a second preferred embodiment, the solvent contained in the liquid phase is selected from non-aqueous organic solvents in which the solubility of Form B at 25° C. and 1013 mbar is not more than 2 wt.%. These organic solvents include in particular aliphatic and cycloaliphatic hydrocarbons and oils, in particular of vegetable origin, as well as C1- _C4 alkyl esters of saturated or unsaturated fatty acids or mixtures of fatty acids, in particular methyl esters, for example methyl oleate, methyl stearate and rapeseed oil methyl ester, as well as paraffinic mineral oils, etc. Accordingly, the present invention also relates to plant protection compositions in the form of a non-aqueous suspension concentrate, which will also be referred to below as OD (oil dispersion).

Such non-aqueous suspension concentrates contain Form B of 1-(1,2-dimethylpropyl)-C-ethyl-5methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide in fine particulate form, wherein Form B particles are suspended in non-aqueous phase. The particle size of the active substance, that is, the size which does not exceed 90% by weight of the particles of the active substance, is in this case usually less than 30 μm, in particular less than 20 μm. Advantageously, in non-aqueous suspension concentrates at least 40% by weight and in particular at least 60% by weight of the particles have a diameter of less than 10 μm.

In such OD, the amount of active substance, i.e. the total amount of 1-(1,2-dimethylpropyl)-C-ethyl5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide and other active substances, if any, generally ranges from 1 to 60% by weight. , in particular, in the range from 5 to 50 wt.%, based on the total weight of the non-aqueous suspension concentrate.

In addition to 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin-4-yl-pyrazol-4-carboxamide and a liquid carrier, non-aqueous suspension concentrates typically contain surfactants and, if necessary, antifoaming agents, rheology modifiers and stabilizers (biocides).

Possible surfactants are preferably the previously mentioned anionic and nonionic surfactants. The amount of surfactants is generally from 1 to 30% by weight, in particular from 2 to 20% by weight, based on the total weight of the non-aqueous SC according to the invention. Preferably, the surfactants include at least one anionic surfactant and at least one nonionic surfactant, and the ratio of anionic to nonionic surfactant is typically in the range of 10:1 to 1:10.

Crystalline Form B according to the invention can also be formulated into solid plant protection formulations. These formulations include powders, dispersants and dusters, as well as water-dispersible powders and granules, such as coated, impregnated and homogeneous granules. Such formulations can be prepared by mixing or simultaneously grinding Form B with a solid carrier and, if necessary, other additives, in particular surfactants. Granules can be obtained by combining the active substances with solid carriers. Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, crushed plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and herbal products such as

- 10 044988 cereal flour, tree bark flour, wood and nut shell flour, cellulose powder or other solid carriers. Solid formulations can also be prepared by spray drying, if necessary, in the presence of polymeric or inorganic drying aids and, if necessary, in the presence of solid carriers. Extrusion, fluid bed granulation, spray granulation and comparable technologies are suitable for the production of Form B solid formulations.

Possible surfactants are the above-mentioned surfactants and protective colloids. The amount of surfactants is generally from 1 to 30% by weight, in particular from 2 to 20% by weight, based on the total weight of the solid composition according to the invention.

In such solid compositions, the amount of active substance, that is, the total amount of tembotrione and other active substances, if necessary, is usually in the range from 10 to 70% by weight, in particular in the range from 20 to 50% by weight, based on the total mass of solid composition.

The following formulations demonstrate the preparation of such formulations of Form B:

I. Water-dispersible powders (WP, SP).

From 50 to 80 wt.% of crystalline Form B according to the invention is ground in a rotor-stator mill with the addition of from 1 to 5 wt.% dispersants, for example sodium lignosulfonate, from 1 to 3 wt.% wetting agents, for example alcohol ethoxylate , and up to 100 wt.% solid carrier, for example, silica gel. When diluted with water, a stable dispersion of Form B is formed.

II. Powder for dusting (DP, DS).

From 1 to 10 wt.% of form B is finely ground and thoroughly mixed with a solid carrier up to 100 wt.%, for example, fine kaolin. In this way, a dusting agent is obtained which contains from 1 to 10% by weight of Form B.

III. Non-aqueous suspension concentrates (OD).

In a ball mill with an agitator, from 20 to 60% by weight of Form B according to the invention is ground into powder with the addition of from 2 to 15% by weight of dispersants and wetting agents, for example calcium dodecylbenzenesulfonic acid and alcohol ethoxylate and optionally sodium salt condensate of urea and formaldehyde phenolsulfonic acid, and up to 100 wt.% paraffinic mineral oil. A stable non-aqueous suspension concentrate of Form B is obtained. When diluted with water, a stable suspension of Form B is obtained.

IV. Aqueous suspension concentrates (SC, FS).

In a ball mill with an agitator, from 20 to 60% by weight of Form B according to the invention is ground into powder with the addition of from 2 to 10% by weight of dispersants and wetting agents, for example sodium lignosulfonate, castor oil ethoxylate and/or alcohol ethoxylate, from 0.1 to 2% by weight of a thickener, for example xanthan gum, optionally other additives such as anti-sedimentation agents, microbiocides and/or antifoaming agents, and up to 100% by weight of water to obtain a fine suspension of the active substance that is stable during storage. When diluted with water, a stable suspension of Form B is formed. For a composition of type FS, up to 40 wt.% of a binder (for example, polyvinyl alcohol) is added.

V. Water-dispersible and water-soluble granules (GR, FG) From 0.1 to 30 wt.% of crystalline form B is finely ground and associated with a solid carrier up to 100 wt.%, for example silicate, in a granulator. Granulation can be achieved, for example, by compression, such as extrusion, or by agglomeration, such as spray drying or fluidized bed granulation.

VI. Aqueous gel formulations (GW, GF).

In a ball mill with an agitator, from 5 to 25 wt.% of Form B are ground into powder with the addition of from 3 to 10 wt.% dispersants, for example, sodium lignosulfonate, from 1 to 5 wt.% thickener, for example, carboxymethylcellulose, and up to 100 wt. .% water to obtain a thin suspension of Form B in a gelled aqueous phase. When the gel is diluted with water, a stable suspension of Form B is formed.

The compositions in accordance with the present invention may contain Form B in accordance with the invention as the only active substance.

However, instead of Form B, a combination of Form B and one or more other agricultural active compounds such as herbicides, insecticides, fungicides, growth regulators, safeners, etc. is used.

The use of Form B or a composition containing Form B is carried out, if the composition is not yet ready for use, in the form of aqueous solutions for spraying. These aqueous spray solutions are prepared by diluting the above formulations containing Form B with water, thus, an aqueous spray solution which contains crystalline Form B. These spray solutions are also part of the present invention. Spray solutions may also contain other components in dissolved, emulsified or suspended form for oils, wetting agents, adjuvants, fertilizers or trace elements, and other active compounds, for example herbicides, insecticides, fungicides, growth regulators, safeners). These agents may be contained in or mixed with the compositions of the invention before use, for example in a weight ratio of 1:100 to 100:1. Typically, these components are added to the spray solution before, during or after dilution of the compositions in accordance with the invention.

Typically, the user applies the composition in accordance with the invention from a pre-metering device, a backpack sprayer, a spray tank, a spray plane or an irrigation system. Typically Form B formulations are diluted with water, buffer and/or other excipients to the desired application concentration. Typically, 20 to 2000 liters, preferably 50 to 400 liters of ready-to-use spray liquid are used per hectare of agricultural land.

As stated above, crystalline Form B of 1-(1,2-dimethylpropyl)-C-ethyl-5-methyl-C-pyridazin4-yl-pyrazol-4-carboxamide and a composition containing it is suitable for the control or suppression of invertebrate pests, in particular , arthropod pests and especially insect pests. Therefore, the present invention also relates to a method for controlling or suppressing invertebrate pests, which includes introducing invertebrate pests, their food resources, including crops, plants and plant propagation materials such as seeds, or their habitats or places into contact propagation, that is, the area, material or environment, such as soil or water, in which invertebrate pests grow or can grow, with crystalline Form B in accordance with the present invention.

Therefore, Crystalline Form B and the composition containing it are equally suitable for use in protecting crops, growing plants and plant propagation materials such as seeds from attack or infestation by invertebrate pests such as insects. Therefore, the present invention also relates to a plant protection method that includes contacting crops, growing plants, plant propagation materials such as seeds, or soil or water in which plants grow to protect against attack or infestation by invertebrates pests, with crystalline Form B according to the present invention.

For further information in this regard, reference is made to WO 2012/143317.

Crystalline Form B according to the present invention is effective both by contact and by ingestion. In addition, crystalline Form B can be applied to many developmental stages such as egg, larva, pupa and adult.

As explained above, crystalline Form B in accordance with the present invention can be used as such or in the form of formulations or aqueous spray solutions containing Form B as described above. In addition, crystalline Form B and the compositions of the present invention can be used together with a mixing component that is typically not another pesticide or adjuvant, or in compositions containing these mixtures as defined above. The components of this mixture can be applied simultaneously, together or separately, or sequentially, that is, immediately one after the other, thus creating an in situ mixture in the desired place, for example, a plant, the sequence, in the case of separate application, as a rule, does not affect no influence on the result of control measures.

Application can be made both before and after pest infestation of crops, plants, plant propagation materials such as seeds, soil or area, material or environment.

Suitable applications include soil treatment, seed treatment, in-furrow application, and foliar application, among others. Tillage methods include soil drenching, drip irrigation (drip application into the soil), root, tuber or bulb immersion, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed drenching and seed pelleting. Typically, furrow application includes the steps of creating a furrow on cropland, sowing the furrow with seeds, applying a pesticide active compound into the furrow, and closing the furrow. Foliar application refers to the application of Form B or a formulation containing it to the foliage of plants, for example, using spray equipment. For foliar application, it may be advantageous to modify pest behavior using pheromones in combination with the compounds of the present invention. Suitable pheromones for specific crops and pests are known to one of ordinary skill in the art and are publicly available from pheromone and chemical signal databases such as http://www.pherobase.com.

As used herein, the term contacting includes both direct contact (applying Form B/formulation directly to the invertebrate pest or plant - typically the foliage, stem or roots of the plant) and indirect contact (applying Form B/formulation to the location, i.e. habitat, breeding site, plant, seed, soil, area, material or environment in which the pest grows or may grow, invertebrate pest or plant).

The term animal pest includes arthropods, gastropods and nematodes.

- 12 044988

Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects that are particularly harmful to crops are commonly referred to as crop pests.

The term crop refers to both growing and harvested crops.

Form B according to the invention and a composition containing Form B are particularly suitable for effective control of animal pests such as arthropods, gastropods and nematodes, including but not limited to:

insects from the order Lepidoptera, for example Achroia grisella, Acleris spp., such as A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp., such as A. cyrtosema, A. or ana; Aedia leucomelas, Agrotis spp., such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Alsophila pometaria, Ampelophaga rubiginosa, Amyelois transitella, Anacampsis sarcitella, Anagasta kuehniella, Anarsia lineatella, Anisota senatoria, Antheraea pernyi, Anticarsia (=Thermesia) spp., such as A. gemmatalis; Apamea spp., Aproaerema modicella, Archips spp., such as A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugella, Argyroploce spp., Argyrotaenia spp., such as A. velutinana; Athetis mindara, Austroasca viridigrisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupaluspiniarius, Busseola spp., Cacoecia spp., such as C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp., such as C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp., such as C. indicus, C. suppressalis, C. partellus; Choreutis pariana, Choristoneura spp., such as C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplusia) spp., such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., CochyUs hospes, Coleophora spp., Colias eurytheme, Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Corcyra cephalonica, Crambus caliginosellus, Crambus teterrellus , Crocidosema ( =Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp., such as C. pomonella, C. latiferreana;

Dalaca noctuides, Datana integerrima, Dasychirapinicola, Dendrolimus spp., such as D. pint, D. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp., such as D. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharalis, Diphthera

- 13 044988 festiva, Earias spp., such as E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curialis, Elasmopalpus lignosellus, Eldana saccharina, Endopiza viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp., such as E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp., such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp., such as G. funebrana, G. molesta, G. inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp., such as H. armigera (=Heliothis armigera), H. zea (=Heliothis zea); Heliothis spp., such as H. assulta, H. subflexa, H. virescens; Hellula spp., such as H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Herpetogramma licarsisalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambd ina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Leguminivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leucoma salicis, Leucoptera spp., such as L. coffeella, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobesia botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp., such as L. sticticalis, L. cereralis; Lymantria spp., such as L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malacosoma spp., such as M. americanum, M. californicum, M. constrictum, M. neustria; Mame str a spp., such as M brassicae, M. configurata; Mamstra brassicae, Manduca spp., such as M. quinquemaculata, M. sexta; Marasmia spp., Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis Ieda, Mods spp., such as M. lapites, M. repanda; Mods latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Operophtera brumata, Orgyiapseudotsugata, Oria spp., Orthaga thyrisalis, Ostrinia spp. , such like O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene regalis, Paysandisia archon, Pectinophora spp., such as P. gossypiella; Peridroma saucia, Perileucoptera spp., such as P. coffeella; Phalera bucephala, Phryganidia californica, Phthorimaea spp., such as P.

- 14 044988 operculella; Phyllocnistis citrella, Phyllonorycter spp., such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp., such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp., such as P. flavedana, P. idaeusalis, P. stultana; Platyptilia carduidactyla, Plebejus argus, Plodia interpunctella, Plusia spp., Plutella maculipennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp., such as P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia mi, Richia albicosta, Rhizobius ventralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura concinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp., such as S. incertulas, S. innotata; Scotia segetum, Sesamia spp., such as S. inferens, Seudyra subflava, Sitotroga cerealella, Sparganothis pilleriana, Spilonota lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp., such as S. cosmoides, S. eridania, S. exigua , S. frugiperda, S. latisfascia, S. littoralis, S. litura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp., such as S. exitiosa, Tecia solanivora, Telehin licus, Thaumatopoea pityocampa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, Theda spp., Theresimima ampelophaga, Thyrinte ina spp, Tildenia inconspicuella, Tinea spp., such as T. cloacella, T. pellionella; Tineola bisselliella, Tortrix spp., such as T. viridana; Trichophaga tapetzella, Trichoplusia spp., such as T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp., such as U. rubigalis, U. rubigalis; Virachola spp., Yponomeutapadella and Zeiraphera canadensis;

insects from the order Coleoptera, for example Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp., such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp., such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimallus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulenta, Anomala rufocuprea, Anoplophora spp., such as A. glabripennis; Anthonomus spp., such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogonia spp., Athous haemorrhoidalis, Atomaria spp., such as A. linearis; Attagenus spp., Aulacophorafemoralis, Blastophaguspiniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp., such as B. lends, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopistria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp., such as C. assimilis, C. napi; Chaetocnema tibialis,

- 15 044988

Cleonus mendicus, Conoderus spp., such as C. vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhynchus lapathi, Ctenicera spp., such as C. destructor;

Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp., such as D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp., such as E. varivestis, E. vigintioctomaculata; Epitrix spp., such as K hirtipennis, E. similaris; Eutheola humilis, Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp., such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lerna spp., such as L. bilineata, L. melanopus; Leptinotarsa spp., such as L. decemlineata; Leptispapygmaea, Limonius californicus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp., such as L. bruneus; Liogenys fuscus, Macrodactylus spp., such as M. subspinosus; Maladera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp., such as M. aeneus;

Melolontha spp., such as L/. hippocastani, M. melolontha; Metamasius hemipterus, Microtheca spp., Migdolus spp., such as M. fryanus, Monochamus spp., such as M. alternatus; Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxycetonia juc unda, Phaedon spp., such as P. brassicae, P cochleariae; Phoracantha recurva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp., such as P. helleri; Phyllotreta spp., such as P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp., such as R. billineatus, R. ferrugineus, R. palmarum , R. phoenicis, R. vulneratus; Saperda candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp., such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp., such as S. levis; Stegobium paniceum

- 16 044988

Sternechus spp., such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp., such as T. castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp., such as

X pyrrhoderus; and Zabrus spp., such as Z. tenebrioides;

insects from the order Diptera, for example, Aedes spp., such as L. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp., such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bactrocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chrysomyia spp., such as C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp., such as C. hominivorax; Contarinia spp., such as C. sorghicola; Cordylobia anthropophaga, Culex spp., such as C. nigripalpus, C. pipiens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasineura oxycoccana, Delia spp., such as D. antique, D. coarctata, D. platura, D. radicum; Dermatobia hominis, Drosophila spp. such as D. suzukii, Fannia spp. such as F. canicular is; Gastraphilus spp., such as G. intestinalis; Geomyza tipunctata, Glossina spp., such as G. fuscipes, G. morsitans, G. palpalis, G. tachinoides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp., such as H. platura; Hypoderma spp., such as H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp., such as L. sativae, L. trifolii; Lucilia spp., such as L. caprina, L. cuprina, L. sericata; Lycoriapectoralis, Mansonia titillanus, Mayetiola spp., such as A/. destructor; Musca spp., such as M. autumnalis, M. domestica; Muscina stabulans, Oestrus spp., such as O. ovis; Opomyza florum, Oscinella spp., such as O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp., such as P. antiqua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp., such as R. cerasi, R. cingulate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp., such as S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp., such as S. calcitrans; Tabanus spp., such as T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodiplosis japonensis, Tipula oleracea, Tipula paludosa and Wohlfahrtia spp;

- 17 044988 insects from the order Fringed Ptera, for example Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp., such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp., such as S. citri, S. dorsalis, S. perseae; Stenchaetothrips spp., Taeniothrips cardamom, Taeniothrips inconsequens, Thrips spp., such as T. imagines, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci;

insects from the order Hemiptera, for example Acizzia jamatonica, Acrosternum spp., such as L. hilare; Acyrthosipon spp., such as L. onobrychis, A. pisum; Adelges laricis, Adelges tsugae, Adelphocoris spp., such as L. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigmapiri, Aphidula nasturtii , Aphis spp., such as L. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A. sambuci, A. schneideri, A. spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacaspisyasumatsui, Aulacorthum solani, Bactericera cockerelli (Paratrioza cockerelli), Bemisia spp., such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp., such as B. leucopterus; Brachycaudus spp., such as B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp., such as C. fulguralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis jug landicola, Chrysomphalus ficus, Cicadulina mbila , Cimex spp., such as C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp., such as C. hesperidum, C. pseudomagnoliarum; Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis, Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbulus spp., Dasynus piper is, Dialeurodes spp., such as D. citrifolii; Dalbulus maidis, Diaphorina spp., such as D. citri; Diaspis spp., such as D. bromeliae; Dichelops furcatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusiapiceae, Drosicha spp., Dysaphis spp., such as

- 18 044988

D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp., such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp., such as E. fabae, E. solana; Epidiaspis leperii, Eriosoma spp., such as E. lanigerum, E. pyricola; Erythroneura spp., Eurygaster spp., such as E. integriceps; Euscelis bilobatus, Euschistus spp., such as E. her os, E. impictiventris, E. servus; Fiorinia theae, Geococcus coffeae, Glycaspis brimblecombei, Halyomorpha spp. such as H. halys; Heliopeltis spp., Homalodisca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, Icerya spp., such as I. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp., such as L. ulmi; Leptocorisa spp., Leptoglossusphyllopus, Lipaphis erysimi, Lygus spp., such as L. hesperus, L. lineolaris, L. pratensis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp., such as M. rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocallis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsispecanis, Myzocallis coryli, Murgantia spp.. Myzu s spp., such as L/. ascalonicus, M. cerasi, M. nicotianae, M. persicae, M. varians; Nasonovia ribis-nigri, Neotoxoptera formosana, Neomegalotomus spp., Nephotettix spp., such as N. malayanus, N. nigropictus, N. parvus, N. virescens; Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius huttoni, Oebalus spp., such as O. pugnax; Oncometopia spp., Ortheziapraelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp., such as P. corni, P. persicae; Pemphigus spp., such as P. bursarius, P. populivenae; Peregrinus maidis, Perkinsiella saccharicida, Phenacoccus spp., such as P. aceris, P. gossypii; Phloeomyzuspasserinii, Phorodon humuli, Phylloxera spp., such as P. devastatrix, Piesma quadrata, Piezodorus spp., such as P. guildinii; Pinnaspis aspidistrae, Pianococcus spp., such as P. citri, P. ficus; Prosapia bicincta, Protopulvinaria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp., such as P. comstocki; Psylla spp., such as P. mali; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp., such as R. pseudobrassicas, R. inserturn, R. maidis, R. padi; Sagatodes spp.,

- 19 044988

Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mail, Scaptocoris spp., Scaphoides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis, Spissistilus fest inus (= Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetr aleur odes perseae, Therioaphis maculate, Thy anta spp., such as T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp., such as T. aurantii;

Trialeurodes spp., such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp., such as U. ci tri, U. yanonensis and Viteus vitifolii, Hymenoptera insects, such as Acanthomyops interjectus, Athalia rosae, Atta spp., such as A capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp., such as C. floridanus, C. pennsylvanicus, C .modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocosmus kuriphilus, Formica spp., Hoplocampa spp., such as H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp., such as L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp., such shM. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinensis, Paratrechina longicornis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp., such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sir ex cyaneus, Solenopsis spp., such as S. geminata, S. invicta, S. molesta, S richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp., such as T. melanocephalum, T. sessile; Tetr amor ium spp., such as T. caespitum, T. bicarinatum, Vespa spp., such as V. crabro; Vespula spp., such as V. squamosal; Wasmannia auropunctata, Xylocopa sp.;

insects from the order Orthoptera, for example, Acheta domesticus, Calliptamus italicus, Chortoicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp., such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp., such as L. migratoria, L. pardalina; Melanoplus spp., such κάκΜ. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris

- 20 044988 septemfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp., such as S. americana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus and

Zonozerus variegatus;

pests from the class of arachnids, for example, acarids, for example, from the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (for example, A. americanum, A. variegatum, A. maculatum), Argas spp., such as L. persicu), Boophilus spp., such as B. annulatus, B. decoloratus, B. microplus, Dermacentor spp., such such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp., such as H. truncatum, Ixodes spp., such as I. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp., such as O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp., such as P. ovis, Rhipicephalus spp., such as R. sanguineus, R appendiculatus, Rhipicephalus evertsi, Rhizoglyphus spp., Sarcoptes spp., such as S. Scabiei', and the families Eriophyidae, including Aceria spp., such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp., such as A. lycopersici, A. pelekassi', Aculus spp., such as A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp., such as Eriophyes sheldoni', families Tarsonemidae, including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp. Steneotarsonemus spinki', families Tenuipalpidae, including Brevipalpus spp., such as B. phoenicis', families Tetranychidae, including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp., such as T. cinnabarinus, T. evansi, T. kanzawai, T, pacificus, T. phaseulus, T. telarius and T. urticae', Bryobiapraetiosa', Panonychus spp., such as P. ulmi, P. citri', Metatetranychus spp. and Oligonychus spp., such as O. pratensis, O. perseae, Vasates lycopersici', Raoiella indica, the family Carpoglyphidae including Carpoglyphus spp.; Penthaleidae spp. such as Halotydeus destructor', family Demodicidae with species such as Demodex spp.; family Trombicidea, including Trombicula spp.; families Macronyssidae including Ornothonyssus spp.; families Pyemotidae, including Pyemotes tritici', Tyrophagus putrescentiae', families Acaridae, including Acarus siro', families Araneida, including Latrodectus mactans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa',

- 21 044988 pests from the nematode phylum, for example plant parasitic nematodes, such as root-knot nematodes, Meloidogyne spp., such as M. hapla, M. incognita, M. javanica; cyst nematodes, Globodera spp., such as G. rostochiensis; Heterodera spp., such as H. avenae, H. glycines, H. schachtii, H. trifolii; gall nematodes Anguina spp.; stem and foliar nematodes, Aphelenchoides spp., such as A. besseyi; sting nematodes, Belonolaimus spp., such as B. longicaudatus; pine nematodes, Bursaphelenchus spp., such as B. lignicolus, B. xylophilus; ring nematodes, Criconema spp., Criconemella spp., such as C. xenoplax and C. ornata; and, Criconemoides spp., such as Criconemoides informis; Mesocriconema spp.; stem and bulb nematodes, Ditylenchus spp., such as D. destructor, D. dipsaci; stink-nosed nematodes, Dolichodorus spp.; spiral nematodes, Heliocotylenchus multicinctus; sheath and tube nematodes, Hemicycliophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; lanceolate nematodes, Hoploaimus spp.; root growth nematodes, Nacobbus spp.; needle nematodes, Longidorus spp., such as L. elongatus; wounding nematodes, Pratylenchus spp., such as P. brachyurus, P. neglectus, P. penetrans, P. curvitatus, P. goodeyi; burrowing nematodes, Radopholus spp., such as R. similis; Rhadopholus spp.; Rhodopholus spp.; kidney nematodes, Rotylenchus spp., such as R. robustus, R. reniformis; Scutellonema spp.; blunt root nematode Trichodorus spp., such as T. obtusus, T. primitivus; Paratricodorus spp., such as P. minor; dwarf nematodes, Tylenchorhynchus spp., such as T. claytoni, T. dubius; citrus nematodes, Tylenchulus spp., such as T. semipenetrans; dagger nematodes, Xiphinema spp.; and other types of nematodes that parasitize plants.

Insects from the order Cockroaches, for example Macrotermes spp., such as M. natalensis; Cornitermes cumulans, Procornitermes spp., Globitermes sulfureus, Neocapritermes spp., such as N. opacus, N. parvus; Odontotermes spp., Nasutitermes spp., such as A. corniger; Coptotermes spp., such as C. formosanus, C. gestroi, C. acinaciformis; Reticulitermes spp., such as R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. virginicus; Heterotermes spp., such as H. aureus, H. longiceps, H. tenuis; Cryptotermes spp., such as C. brevis, C. cavifrons; Incisitermes spp., such as /, minor, I. snyderi; Marginitermes hubbar di, Kalotermes flavicollis, Neotermes spp., such as N.

- 22 044988 castaneus, Zootermopsis spp., such as Z. angusticollis, Z. nevadensis, Mastotermes spp., such as M. darwiniensis; Blatta spp., such as B. orientalis, B. lateralis;

Blattella spp., such as B. asahinae, B. germanica; Rhyparobia maderae, Panchlora nivea, Periplaneta spp., such as P. americana, P. australasiae, P. brunnea, P. fuliginosa, P. japonica; Supella longipalpa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis.

Insects from the order Fleas, such as Cediopsylla simples, Ceratophyllus spp., Ctenocephalides spp., such as C.felis, C. canis, Xenopsylla cheopis, Pulex irritans, Trichodectes canis, Tunga penetrans and Nosopsyllus fasciatus.

Insects from the bristletail order, such as Lepisma saccharina, Ctenolepisma urbana and Thermobia domestica.

Pests from the class of labiopods, for example, Geophilus spp., Scutigera spp., such as Scutigera coleoptrata;

Pests from the class Dipopods, for example, Blaniulus guttulatus, Julus spp., Narceus spp.

Pests from the symphylum class, for example, Scutigerella immaculata.

Insects from the order Leatheroptera, for example, Forficula auricularia.

Insects from the order Forktail, such as Onychiurus spp., such as Onychiurus armatus.

Pests from the order Isopods, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber.

Insects from the order of lice, for example, Damalinia spp., Pediculus spp., such as Pediculus humanus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp., such as Haematopinus eurysternus, Haematopinus suis; Linognathus spp., such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.

Examples of other pest species that can be controlled using compounds of formula (I) include: from the phylum Mollusca, class Bivalves, for example, Dreissena spp.; class Gastropods, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; from the class of helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi,

- 23 044988

Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp.,

Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., such as Haemonchus contortus;

Heterakis spp., Hymenolepis papa, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora Us, Stronyloides spp. ., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.

In the context of the present invention, the term crop refers to both growing and harvested crops.

In the context of the present invention, the term plant includes cereals, for example, durum wheat and other varieties of wheat, rye, barley, triticale, oats, rice or corn (fodder corn and sweet corn/sweet and field corn); beets, such as sugar beets or fodder beets; fruit plants such as pome fruits, stone fruits or berry fruits, for example apples, pears, plums, peaches, nectarines, almonds, cherries, papaya, strawberries, raspberries, currants or gooseberries; legumes such as lentils, peas, alfalfa or soybeans; oilseeds, such as rapeseed, turnip, mustard, olive, sunflower, coconut, cocoa bean, castor bean, oil palm, ground nuts or soybeans; pumpkins, such as pumpkin, pumpkin, cucumbers or melons; fibrous plants such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapefruits or tangerines; vegetable plants such as eggplant, spinach, lettuce (eg iceberg lettuce), endive, cabbage, asparagus, cabbage plants, carrots, onions, garlic, leeks, tomatoes, potatoes, pumpkin or capsicums; bay plants such as avocado, cinnamon or camphor; energy and raw material plants such as corn, soybeans, rapeseed, sugar cane or oil palm; tobacco; nuts, such as walnuts; pistachio nut; coffee; tea; bananas; grapes (table grapes and grapes for juice and wine); hop; sweet grass (also called stevia); natural rubber plants or ornamental and forest plants such as flowers (eg carnations, petunias, geraniums/pelargoniums, pansies and impatiens), shrubs, broadleaf trees (eg poplar) or evergreens such as conifers; eucalyptus; sod; lawn grasses; grass, such as grass for animal feed or ornamental use. Preferred plants include potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, canola, legumes, sunflowers, coffee or sugar cane; fruit; grape; ornamental plants; or vegetable crops such as cucumbers, tomatoes, beans or pumpkins.

As used herein, the term crop plants also includes plants that have been modified by mutagenesis or genetic engineering to impart a new trait to the plant or to modify an existing trait.

Mutagenesis includes random mutagenesis techniques using X-ray or mutagenic chemicals, as well as site-directed mutagenesis techniques to create mutations at a specific locus in the plant genome. Site-directed mutagenesis techniques often use oligonucleotides or proteins such as CRISPR/Cas, zinc finger nucleases, TALENs, or meganucleases to achieve the target effect.

Genetic engineering typically uses recombinant DNA techniques to create modifications in the plant genome that would not normally be readily produced by crossing, mutagenesis, or natural recombination. Typically, one or more genes are integrated into a plant's genome to add a trait or improve a trait. These integrated genes are also called transgenes in the art, with plants containing such transgenes being called transgenic plants. The process of plant transformation usually results in several transformation events that differ in the genomic locus at which the transgene is integrated. Plants containing a particular transgene at a particular genomic locus are usually described as involving a particular event, which is known by a particular event name. Traits that have been introduced or modified into plants include, but are not limited to, herbicide tolerance, insect resistance, increased yield, and tolerance to abiotic conditions such as drought.

Herbicide resistance has been created through mutagenesis as well as genetic

- 24 044988 engineering. Plants that have been rendered resistant to acetolactate synthase (ALS) inhibitor herbicides by conventional mutagenesis and selection techniques include plant varieties commercially available under the name Clearfield®. However, most herbicide resistance traits have been engineered using transgenes.

Herbicide resistance has been developed to glyphosate, glufosinate, 2,4-D, dicamba, oxynyl herbicides such as bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides, and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors such as isoxaflutole and mesotrione.

Transgenes that have been used to provide herbicide resistance traits include: for glyphosate resistance: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for glufosinate resistance: pat and bar, for 2,4 resistance -D: aad-1 and aad-12, for dicamba resistance: dmo, for oxynyl herbicide resistance: bxn, for sulfonylurea herbicide resistance: zm-hra, csr1-2, gm-hra, S4-HrA, for resistance to ALS herbicide inhibitors: csr1-2, for resistance to HPPD herbicide inhibitors: hppdPF, W336 and avhppd-03.

Transgenic corn events containing herbicide resistance genes are, for example, but not exclusive to others: DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, M ZHG0JG,HCEM485, VCO-01981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.

Transgenic soybean events containing herbicide resistance genes are, for example, but not exclusive to others: GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.

Transgenic cotton events containing herbicide resistance genes are, for example, but not exclusive to others: 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224 , MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.

Transgenic canola events containing herbicide resistance genes are, for example, but not exclusive to others: MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.

Insect resistance has largely been created by transferring bacterial genes for insecticidal proteins to plants. The most commonly used transgenes are the Bacillus spec. toxin genes. and their synthetic variants, such as cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20. However, plant-derived genes have been transferred to other plants. In particular, genes encoding protease inhibitors such as CpTI and pinII. Another approach uses transgenes to produce double-stranded RNA in plants to target and down-regulate insect genes. An example of such a transgene is dvsnf7.

Transgenic corn events containing genes for insecticidal proteins or double-stranded RNA, such as, but not excluding others: Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 53 07, 59122, TS1507 , TS6275, SVN-351, MIR162, DBT418 and MZIR098.

Transgenic soybean events containing insecticidal protein or double-stranded RNA genes, such as but not limited to: MON87701, MON87751 and DAS-81419.

Transgenic cotton events containing genes for insecticidal proteins or double-stranded RNA, such as, but not excluding others: SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, event 1, COT67 V, SOT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.

Increased yield was obtained by increasing ear biomass using the athb17 transgene present in the maize event MON87403 or by enhancing photosynthesis using the bbx32 transgene present in the soybean event MON87712.

Oil-modified crop plants were created using the transgenes: gm-fad2-1, PJ.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events containing at least one of these genes are: 260-05, MON87705 and MON87769.

Abiotic tolerance, particularly drought tolerance, was generated using the cspB transgene contained in the maize event MON87460 and using the Hahb-4 transgene contained in the soybean event IND-00410-5.

Traits are often combined by combining genes in a transformation event or by combining different events during reproduction. The preferred combination of traits is herbicide resistance to different groups of herbicides, resistance to various types of insects, in particular resistance to Lepidoptera and Coleoptera insects, herbicide resistance with one or more types of insect resistance, herbicide resistance together with increased yield, and also a combination of herbicide resistance and resistance to abiotic conditions.

Plants having singular or pyramidal traits, as well as the genes and events that provide these traits, are well known in the art. For example, detailed information on mutagenized or integrated genes and related events is available on the websites of the International Service for the Acquisition of AgrI.biotech Applications (ISa) (http://www.isaaa.org/gmapprovaldatabase) and the Center for Environmental Risk Assessment (CERA) (http://cera-gmc.org/GMCropDatabase). Additional information on specific events and how to detect them can be found for canola events MS1, MS8, RF3, GT73, MON88302, KK179 in WO 01/031042, WO 01/041558, WO 01/041558, WO 02/036831, WO 11/153186 , WO 13/003558, for cotton events MON1445, MON15985, MON531(MON15985), LLCotton25, MON88913, SOT102, 281-24236, 3006-210-23, SOT67V, GHB614, T304-40, GHB119, MON88701, 81910 in WO 02 /034946, WO 02/100163, WO 02/100163, WO 03/013224, WO 04/072235, WO 04/039986, WO 05/103266, WO 05/103266, WO 06/128573, WO 07/0171 86, WO 08 /122406, WO 08/151780, WO 12/134808, WO 13/112527, for corn events GA21, MON810, DLL25, TC1507, MON863, MIR604, LY038, MON88017, 3272, 59122, NK603, MIR 162, MON89034, 98140, 32138 , MON87460, 5307, 4114, MON87427, DAS40278, MON87411, 33121, MON87403, MON87419 in WO 98/044140, US 02/102582, US 03/126634, WO 04/099447, WO 04/011601, WO 05/103301, WO 05/061720, WO 05/059103, WO 06/098952, WO 06/039376, US 2007/292854, WO07/142840, WO 07/140256, WO 08/112019, WO 09/103049, WO 09/1 11263, WO 10 /077816, Wo 11/084621, Wo 11/062904, Wo 11/022469, Wo 13/169923, Wo 14/116854, Wo 15/053998, Wo 15/142571, for potatoes E12, F10, J3, J55, V1111111 , X17, Y9 in WO 14/178910, WO 14/178913, WO 14/178941, WO 14/179276, WO 16/183445, WO 17/062831, WO 17/062825, for rice events LLRICE06, LLRICE601, LLRICE62 in WO 00/026345, WO 00/026356, WO 00/026345 for soybean events H7-1, MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701, MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712 , SYHT0H2, DAS81419, DAS81419 x DAS44406-6, MON87751 in WO 04/074492, WO 06/130436, WO 06/108674, WO 06/108675, WO 08/054747, WO 08/002872, WO 09/064652, WO 9 /102873, WO 10/080829, WO 10/037016, WO 11/066384, WO 11/034704, WO 12/051199, WO 12/082548, WO 13/016527, WO 13/016516, WO 14/2012 35.

The use of Form B in crop plants may result in effects specific to the crop plant containing a particular gene or event. These effects may include changes in growth behavior or changes in resistance to biotic or abiotic stressors. Such effects may include, but are not limited to, increased yield, increased resistance or tolerance to insect, nematode, fungal, bacterial, mycoplasma, viral or viroid pathogens, as well as early vigor, early or delayed ripening, resistance to cold or heat, and also an altered spectrum or content of amino acids or fatty acids.

Surprisingly, it has been found that the pesticidal activity of Form B can be enhanced by the insecticidal trait of the modified plant. In addition, the compounds of the present invention have been found to be suitable for preventing insect resistance to an insecticidal trait or for controlling pests that have already become resistant to the insecticidal trait of a modified plant. Moreover, Form B may be suitable for controlling pests against which the insecticidal trait is not effective, so that additional insecticidal activity can be advantageously used.

The term plant propagation material refers to all the generative parts of a plant, such as seeds and vegetative plant material, such as cuttings and tubers (eg potatoes), that can be used to propagate the plant. It covers seeds, roots, fruits, tubers, bulbs, rhizomes, sprouts, shoots and other parts of plants, including seedlings and young plants that must be replanted after germination or after emerging from the soil. These plant propagation materials may be treated prophylactically with a plant protection compound either during or before planting or transplanting.

The term seed covers the seeds and cuttings of plants of all kinds, including, but not limited to, whole seeds, parts of seeds, side shoots, corms, bulbs, fruits, tubers, grains, cuttings, cuttings and the like, and is preferably means whole seeds.

One skilled in the art will appreciate that Form B will be applied in a pesticidal effective amount. Generally, the term pesticidal effective amount means the amount of Form B or a mixture with another pesticide necessary to achieve a visible effect on growth, including the effects of necrosis, death, stunting, prevention and removal, destruction or other reduction in the number and activity of the target organisms. The pesticide effective amount may vary for different compounds/compositions used in the invention. The pesticidal effective amount of the composition also depends on prevailing conditions, such as the desired pesticidal action and its duration, weather, target species, location, method

- 26 044988 applications, etc.

In the case of soil treatment, furrow application or application to pest habitats or breeding grounds, the amount of active substance is in the range from 0.0001 to 500 g per 100 m ² , preferably from 0.001 to 20 g per 100 m ² .

For crop applications, such as foliar application, the application rate of Form B may range from 0.0001 g to 4000 g per hectare, for example from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare. hectare, preferably 1 g to 100 g per hectare, more preferably 10 g to 50 g per hectare, for example 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, or from 40 to 50 g per hectare.

Form B according to the present invention and plant protection compositions containing Form B are particularly suitable for use in seed treatments to protect seeds from insect pests, in particular soil-borne insect pests, and emerging roots and shoots of seedlings from insects. in particular from soil and foliar insects. Therefore, the invention also relates to a method for protecting seeds from insects, in particular from soil insects and roots, and seedling shoots from insects, in particular from soil and foliar insects, this method includes treating the seeds before sowing and/or after pre-germination connection according to the invention. Preference is given to protecting the roots and shoots of seedlings. It is more preferable to protect seedling shoots from stinging and sucking insects, chewing insects and nematodes.

The term seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed drenching, seed pelleting and in-furrow methods. Preferably, seed treatment with the active compound is carried out by spraying or dusting the seeds before sowing the plants and before the plants emerge.

The present invention also covers seeds coated with or containing the active compound. The term coated and/or containing generally means that the active substance is present on the majority of the surface of the propagation product during application, although more or less of the substance may penetrate into the propagation product depending on the method of application. When said propagation product (replanted) is planted, it can absorb the active substance.

Suitable seeds are, for example, seeds of cereals, root crops, oilseeds, vegetables, spices, ornamental plants, for example seeds of durum and other wheat, barley, oats, rye, corn (fodder corn and sweet corn/sweet and field corn) , soybeans, oilseeds, cruciferous crops, cotton, sunflowers, bananas, rice, oilseed rape, oilseed turnips, sugar beets, fodder beets, eggplant, potatoes, grass, lawn grass, turf, forage grass, tomatoes, leeks, pumpkin pumpkins, cabbage, iceberg lettuce, peppers, cucumbers, melons, Brassica spp., melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugarcane, tobacco, grapes, petunias, geraniums/pelargoniums , pansies and impatiens.

In addition, Form B can also be used to treat seeds from plants that have been modified by mutagenesis or genetic engineering and that are, for example, resistant to herbicides or fungicides or insecticides. Such modified plants have been described in detail above.

Common seed treatment formulations include, for example, FS flowable concentrates, LS solutions, suspoemulsions (SE), DS dry treatment powders, WS water-dispersible suspension treatment powders, SS water-soluble powders, and ES and EC emulsions and gel formulations. G.F. These formulations can be applied to seeds diluted or undiluted. Application to seeds is carried out before sowing, or directly to the seeds, or after the seeds have been previously germinated. Preferably, the compositions are applied in such a way that germination does not occur.

The concentrations of active substances in the ready-to-use formulations containing crystalline Form B, which can be obtained after two- to ten-fold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40% by weight.

In a preferred embodiment, the FS formulation is used to treat the seeds. Typically, such an FS composition contains from 1 to 800 g/l active substance, from 1 to 200 g/l surfactant, from 0 to 200 g/l antifreeze, from 0 to 400 g/l binder, from 0 to 200 g/l pigment and up to 1 liter of water.

The following illustrations and examples serve to illustrate the invention and should not be construed as limiting.

Figures.

In fig. 1 shows the X-ray powder diffraction pattern of Form B obtained from Example 1 using analytical protocol 1.1.

In fig. Figure 2 shows the X-ray powder diffraction pattern of Form A obtained from

- 27 044988 comparative example 1 using analytical protocol 1.1.

In fig. Figure 3a shows superimposed X-ray powder diffraction patterns of the shape.

A (top) and form B (bottom).

In fig. Figure 3b shows, on an enlarged scale, superimposed X-ray powder diffraction patterns of Form A (top) and Form B (bottom) in the 2θ range 14 - 26°.

In fig. Figure 4a shows a semi-quantitative solid-state ¹³ C NMR spectrum of Form B obtained from Example 1 using analytical protocol 1.5(a). The numbers above the peaks indicate the chemical shift as a function of TMS.

In fig. 4b shows a quantitative solid-state ¹³ C NMR spectrum of Form B obtained from Example 1 using analytical protocol 1.5(b) in the region from 50 to 0 parts. per million. The numbers above the peaks indicate the chemical shift as a function of TMS. The numbers below the peaks are integrals standardized to 100%.

In fig. 5a shows a semi-quantitative solid-state ¹³ C NMR spectrum of Form A obtained from Comparative Example 1 using analytical protocol 1.5(a). The numbers above the peaks indicate the chemical shift as a function of TMS.

In fig. 5b shows a quantitative solid-state ¹³ C NMR spectrum of Form B obtained from Comparative Example 1 using analytical protocol 1.5(b) in the region from 50 to 0 parts. per million. The numbers above the peaks indicate the chemical shift as a function of TMS. The numbers below the peaks are integrals standardized to 100%.

In fig. Figure 6 shows the unit cell crystal structure of Form B. The hydrogen atoms are not shown.

Analytical protocols.

1.1. Powder X-ray diffraction (XRD).

Laboratory PRD patterns were recorded using a PANalytical X'Pert Pro X-ray diffractometer using Cu Ka radiation in reflection geometry (Bragg-Brentano). The sample is placed in a 0.2 mm deep single crystal silicon sample holder and aligned carefully and accurately. The tube voltage is 45 kV and the current is 40 mA. PRD data are collected at room temperature in the range from 2θ =3.0°-40.0° in increments of 0.017° and measurement times from 20 to 200 s/step.

1.2. Thermogravimetry (TGM).

THM data were recorded using a TG/DTA 7200 (SII Nano Technology Inc). The samples were placed in standard platinum cuvettes. The sample size in each case ranged from 2 to 10 mg. The heating rate was 10°C/min. During the experiment, the samples were blown with a stream of synthetic air.

1.3. Dynamic scanning calorimetry (DSC) DSC data were recorded using a Mettler Toledo DSC 823e/700/229 module. The samples were placed in standard aluminum cuvettes. The sample size in each case ranged from 1 to 10 mg. The heating rate was 10°C/min. During the experiment, the samples were purged with a nitrogen stream. The point at which the endothermic phenomenon begins is indicated as the melting point.

1.4. X-ray diffraction on a single crystal.

A single crystal with dimensions as described in Example 3 was prepared and subjected to single crystal X-ray diffraction for structure analysis. X-ray diffraction data were collected on a Bruker AXS 8D Pro-spector diffractometer at 100 K using CuKa radiation (1.5418 A). The images were processed using Saint (from Bruker AXS) and the structure was solved using SHELXS and refined using SHELXL.

1.5. Solid-state nuclear magnetic resonance (NMR) spectroscopy.

Solid state NMR spectra of Form A and Form B were obtained under the following experimental conditions: 14.1 T magnet (i.e. 600 MHz Larmor frequency), Bruker Avance Neo spectrometer with 3.2 mm Magic Angle Spinning probe, zirconium rotors with Vespel covers, samples completely fill the rotors, Magic Angle Spinning speed 10 kHz (ω/2π);

(a) cross-polarization experiment: 3.5 μs 1H 90° pulse followed by 3 ms cross-polarization 1H- ^13C at 50 kHz ^13C and approx. 60 kHz (ramp +/- 10%) H RF spin sync, with at least 512 scans with 2 s recycle delay;

(b) single-pulse experiment: direct polarization ¹³ C with a 90° pulse of 5 μs, registration of the decay of free induction at 71 kHz proton heteronuclear dipolar decoupler TRRM-15 for 17 ms, at least 256 scans with a recycle delay of 300 s.

Fourier transform processing with 5 Hz exponential line expansion and manual zero- and first-order baseline correction. Resonance frequencies are given relative to tetramethylsilane (TMS) in deuterated chloroform at 1% volume fraction at magic angle rotation, through solid adamantane as a secondary standard with C methylene resonance at 37.77 parts. per million, according to [IUPAC 2008] Eq. (6).

1.6. Particle size measurement.

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Particle size measurements of aqueous suspensions of Forms A and B were carried out by dynamic light scattering using a Malvern Mastersizer 3000. Before measurement, samples were diluted with a saturated aqueous solution of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4- yl-pyrazol-4carboxamide to a solids content of about 0.1-1 wt%.

1.7. Viscosity.

The SC viscosity of Forms A and B was determined at 20°C and shear rates from 1 to 200 s ^-1 using an Anton Paar Physica MCR 301 rheometer.

.8. Microscopy.

Microscopic analysis of SC formulations of Forms A and B was carried out at 50x magnification using a Nikon Eclipse ME600 microscope.

Preparation of forms A and B by crystallization from an organic solvent

1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide, having a purity of >90%, can be prepared by reacting 4-ethylaminopyridazine with 1-(1 ,2-dimethylpropyl)-5methyl-pyrazole-4-carbonyl chloride in dichloromethane in the presence of trimethylamine, analogous to the protocol of example 1 from WO 2012/143317.

Example 1.

In a glass test tube with a stirrer, 450 mg of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-Npyridazin-4-yl-pyrazol-4-carboxamide was dissolved in 3 ml of dry ethyl acetate (analytical grade) at 70°C . The solution was left for 1 hour at 70°C until completely dissolved. The solution was cooled while stirring at a controlled cooling rate of 5°C/h. up to 0°C. Thus, small crystals were formed, which were separated from the mother liquor and analyzed by powder X-ray diffractometry (XRD). The X-ray diffraction pattern is shown in Fig. 1. Solid-state ¹³ C NMR spectra of the material relative to standard tetramethylsilane (TMS, 1% in CDCl ₃ ) showed the characteristic shifts indicated above for Form B.

Example 2.

In a glass test tube with a stirrer, 250 mg of 1-(1,2-dimethylnponyl)-N-ethyl-5-methyl-Npyridazin-4-yl-pyrazol-4-carboxamide was dissolved in 3 ml of a mixture of 1 ml of n-butyl acetate (analytical grade ) and 2 ml n-heptane (analytical grade) at 70°C. The mixture was left for 1 hour at 70°C until completely dissolved. This formed small crystals, which were separated from the mother liquor and analyzed using powder X-ray diffractometry (XRD) and DSC. Based on the characteristic reflections, form B was identified.

Example 3.

Crystals suitable for single crystal diffraction experiments can be obtained by slow solvent evaporation from a solution of Form B in ethyl acetate at room temperature, as demonstrated by powder X-ray diffractometry.

Example 4.

100 mg of crystalline Form B obtained according to the protocol of Example 1 was ground for 5 minutes using a mortar and pestle. The crystalline mass was analyzed by powder X-ray diffractometry. The shape was identified by characteristic reflections.

A sample of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide, which was identified as highly pure crystalline form B by XRD, was analyzed by solid state ¹³ With NMR, THM and DSC. In fig. 4a and 4b show solid-state ¹³ C NMR of this sample. The melting point of the sample, determined by DSC, was 89°C; the heat of fusion, determined by DSC, of this sample was approximately 98 to 100 J/g. THM showed that when heated to 200°C, there was no loss of material.

Comparative example 1.

1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide was prepared using the protocol of Example 1 of WO 2012/143317. Removal of the chromatographic solution to dryness resulted in the formation of a glassy material, which was analyzed by powder X-ray diffractometry (XRD), solid-state ¹³ C NMR, THM and DSC. The diffraction pattern of the material is shown in Fig. 2. The data shows that the material corresponds to Form A. The melting point was 87°C. THM showed that when heated to 200°C, there was no loss of material.

Solid state ¹³ C NMR spectra of the material relative to standard tetramethylsilane (TMS, 1% in CDCl ₃ ) showed the characteristic shifts shown above for Form A. The spectra are depicted in FIG. 5a and 5b.

Comparative example 2.

1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide was prepared using the protocol of example 2 of WO 2012/143317. Removal of the chromatographic solution to dryness resulted in the formation of a glassy material, which was analyzed by powder X-ray diffractometry (XRD) and DSC. Form A was identified from characteristic reflections. The melting point was 87°C.

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Comparative examples 3.1-3.6.

mg of form B was dissolved in 1 ml of the appropriate solvent at 60°C. At this temperature, the solvent was evaporated under a nitrogen stream. The solvents were methanol, isopropanol, dimethylformamide,

3-methylpentan-2-one, N-methylpyrrolidone and pyridine. Based on the characteristic reflections, form A was identified.

Example 5.

In a glass tube with a stirrer, 50 mg of Form A and 50 mg of Form B were suspended in 1 ml of water and stirred for 5 days at room temperature. The resulting solid was removed from the mother liquor and analyzed by PRD. The PRD corresponds to the data for crystal form B.

Preparation of the aqueous suspension concentrate composition (SC composition) of forms A and B.

Example 6.

1-(1,2-Dimethylpronyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide Form B was prepared as an aqueous suspension concentrate formulation (SC formulation) having the following general composition, given in table. 3:

Table 3

Substance g/l Form B 220.0 Surfactant 84.4 Dispersant 21.1 Anti-precipitant 10.6 Anti-Songwriter 4.2 Preservative 1 2.1 Preservative 2 1.1 Thickener 1.4 Acetic acid 1.1 Water up to 1 l

Surfactant: castor oil ethoxylate containing an average of 40 ethylene oxide units per molecule.

Dispersant: lignosulfonate - Greensperse® S9 from Borregard Lignotech anti-settling agent: hydrophobic pyrogenic silica - Aerosil R 972 from Evonik.

Antifoam: aqueous silicone emulsion - Silfoam® SRE from Wacker Preservative 1: 20% aqueous suspension of benzisothiazolone Preservative 2: aqueous composition of 5-chloro-2-methyl-2H-isothiazol-3-one and 2methyl-2H-isothiazol-3-one ( 3:1) - Acticide MV from Thor Chemie.

Thickener: xanthan gum.

Form B was mixed with a surfactant, a dispersant, a part of an antifoam and a part of water. The mixture was then ground in a ball mill with a sufficient load of balls to ensure efficient grinding. The temperature of the grinding head was maintained at 5°C. Grinding was stopped when an average particle size of approximately 2 μm was reached (visually assessed using a Nikon Eclipse ME600 microscope at 50× magnification). To the suspension thus obtained, the remaining antifoam, preservative, thickener and remaining water were added with stirring to ensure uniform distribution of the components. The amount of water was chosen such that the final concentration of 1-(1,2-dimethylpropyl)-Nethyl-5methyl-L-pyridazin-4-yl-pyrazol-4-carboxamide in the formulation was 220 g/L.

The viscosity of the freshly prepared SC composition, determined at 20 °C and a shear rate of 100 s ^-1 , was 56.4 mPa-s.

Comparative example 4.

Following the protocol of Example 6, 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-Npyridazin-4-yl-pyrazol-4-carboxamide Form A was prepared as an aqueous suspension concentrate formulation (SC formulation) having same general composition as Example 6 except that Form B has been replaced by Form A.

The viscosity of the freshly prepared SC composition, determined at 20°C and a shear rate of 100 s ^-1 was 52.1 mPa-s. The initial particle size was assessed visually using a Nikon Eclipse ME600 microscope at 50x magnification.

Assessment of storage stability.

Samples of the respective formulations were stored for 12 weeks at -10°C and freeze-thaw cycled from -10°C to 30°C every 48 hours (FT). After storage, the particle size distribution and viscosity of the samples were determined as described above. The results are presented in the following tables. 4 and 5:

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Claims (11)

Table 4 Table 5 Particle size distribution after storage at -10°C Particle size distribution after storage at FT D _v (50) [µm] D _v (90) [µm] D _v (50) [µm] D _v (90) [µm] Example 6 2.09 6.17 2.33 8.92 Comparative example 4 3.02 9.48 5.25 17.2 Viscosity at 20°C and 100 s' ¹ initial After storage at -10°C After storage at FT Example 6 56.4 68.0 58.3 Comparative example 4 52.1 74.0 66.8 In addition, the corresponding samples were analyzed using a microscope. To do this, three samples were taken from each sample and analyzed under a microscope for the formation of large particles. Samples of the SC composition from example 6 did not contain particles larger than 10 μm. In contrast, samples of the SC formulation of Comparative Example 4, which were stored under freeze-thaw conditions, showed significant particle growth with a large number of particles ranging in size from 10 to 50 μm. The results indicate that formulations containing Form A may become unstable during storage due to particle size growth. CLAIM 1. Crystalline form B of 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4carboxamide, which displays 3 in the X-ray powder diffraction diagram at 25°C and CuKa radiation the following reflections given as 2θ values: 20.69±0.10°, 24.15±0.10° and 30.52±0.10°. 2. Crystal form B according to claim 1, which in the X-ray powder diffraction pattern at 25°C and Cu-Ka radiation additionally displays at least one of the following reflections, indicated as 2θ values: 10.07±0.10°, 15.31±0.10°, 15.97±0.10°, 16.50±0.10°, 19.29±0.10°, 20.22±0.10°, 20.96±0.10° and 26.09±0.10° and which optionally further displays at least one of the following reflections specified as 2θ values: 7.99±0.10 °, 12.38±0.10°, 18.03±0.10°, 23.40±0.10°, 23.70±0.10°, 27.26±0.10° and 32.91±0.10°. 3. Crystalline form B according to any of the previous paragraphs, wherein form B is monoclinic with space group P2 _b 4. Crystalline form B according to any of the previous paragraphs, which in ^{the 13} C solid-state NMR spectrum shows the following peaks: 165.3 ± 0.3, 152.7 ± 0.3, 149.9 ± 0.3, 141.9 ± 0.3, 141.1 ± 0.3, 119.7 ± 0.3, 118.9 ± 0.3, 113.8±0.3, 61.2±0.3, 60.4±0.3, 39.8±0.3, 32.9±0.3, 31.9±0.3, 21.4±0.3, 19.4±0.3, 17.9±0.3, 16.3±0.3, 12.8±0.3, 9.4±0.3 and 9 .0± 0.3 part. per million 5. Crystalline Form B according to any of the preceding claims, containing at least 94% by weight of 1-(1,2dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide. 6. Solid 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide, consisting of at least 90% by weight of crystalline Form B according to any one of paragraphs 1-5. 7. A plant protection composition containing crystalline form B of 1-(1,2-dimethylpropyl)-Nethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide according to any one of claims 1 to 5 and one or several carriers customary for the preparation of plant protection compositions. 8. A plant protection composition containing 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin4-yl-pyrazol-4-carboxamide and one or more carriers customary for the preparation of plant protection compositions wherein 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4carboxamide consists of at least 90% by weight of crystalline form B according to any one of claims 1 -5. 9. A plant protection composition according to any one of claims 7 or 8, which is in the form of an aqueous suspension concentrate or in the form of a non-aqueous suspension concentrate. 10. Plant protection composition according to any one of claims 7 or 8 in the form of a powder or in the form of granules dispersible in water. 11. Use of crystalline form B of 1-(1,2-dimethylpropyl)-H-ethyl-5-methyl-K-pyridazin-4yl-pyrazol-4-carboxamide according to any one of claims 1 to 5 or a plant protection composition according to any from claims 7-10 for the control or suppression of invertebrate pests. -