Solid form of a quinoline carboxamide compound

Abstract

The present invention relates to a racemic crystalline form of the compound of formula (I) which has a powder X-ray diffraction pattern comprising at least three 2θ angle values selected from the group consisting of 8.0 ± 0.2°, 8.4 ± 0.2°, 10.0 ± 0.2°, 10.6 ± 0.2°, 10.8 ± 0.2°, 11.9 ± 0.2°, 13.2 ± 0.2°, 14.2 ± 0.2°, 15.2 ± 0.2°, 15.3 ± 0.2°, 16.0 ± 0.2°, 16.5 ± 0.2°, 17.0 ± 0.2°, 17.6 ± 0.2°, and 17.9 ± 0.2°.

Description

[0001] SOLID FORM OF A QUINOLINE CARBOXAMIDE COMPOUND

[0002] This invention relates to a solid form of a quinoline carboxamide derivative, a process to prepare said solid form, to a composition comprising said solid form, and to a method of its use as fungicide.

[0003] WO 2017 / 153380 discloses that certain quinoline carboxamide derivatives have a microbicidal activity, such as a fungicidal activity. In particular, a compound of formula I is disclosed: N-(1-benzyl-1 ,3- dimethyl-butyl)-8-fluoro-quinoline-3-carboxamide:

[0004] Mixtures of this compound with other fungicides are disclosed in WO 2019 / 052930, as well as processes for the preparation of quinoline carboxamide derivatives have been disclosed.

[0005] Compound of formula (I) has two enantiomers: compounds (l-R) and (l-S), shown below:

[0006] CAS 2132414-06-1 CAS 2132414-05-0

[0007] (l-R) (l-S)

[0008] In particular, Feneptamidoquin is a mixture of 80% to 100% of compound of formula (l-R) and 0% to 20% of compound of formula (l-S), the total being equal to 100%. Feneptamidoquin may also be defined as N-[(1 RS)-1 ,3-dimethyl-1-(phenylmethyl)butyl)]-8-fluoro-3-quinolinecarboxamide (compound of formula I), containing 80-100% of the R-enantiomer (i.e. compound of formula l-R), or as N-[(1 RS)- 1 ,3-dimethyl-1-(phenylmethyl)butyl)]-8-fluoro-3-quinolinecarboxamide, containing up to 20% of the S- enantiomer (i.e. compound of formula l-S).

[0009] A solid form of compound of formula (l-R) and its preparation have been described in WO 2024 / 246265. The crystalline form of the compound of formula (l-R) is designated as Form A. Its characterisation is given in Example 1 . Different enantiomers have the same physical properties so they will have the same polymorphs. A solid form of compound (l-S) has the same properties as solid Form A of compound (l-R).

[0010] It has also been found that when compounds (l-R) and (l-S) are present together, they may combine and form a conglomerate racemic solid form, which is designated as Form RAC. The crystalline Form RAC causes crystal growth in aqueous suspensions. When formulating a compound of formula I, such as Feneptamidoquin, it is desirable to limit crystal growth.

[0011] It is important to avoid crystal growth in agrochemical compositions due to the potential adverse effects on application uniformity, handling, effectiveness, safety, and product quality. Usually, agrochemical compositions are provided as concentrates. The end-user will dilute these concentrates prior to application. As a consequence, crystal growth may cause handling and mixing difficulties to the end-user. In addition, if crystals are larger than expected, they can lead to clogging of the application equipment (usually sprayers), such as pipes, tubes and nozzles. This may result in an uneven distribution of active ingredients, with higher rates in some areas and lower rates in others. In turn, the effectiveness of the active ingredient may be reduced.

[0012] Methods to screen solid state forms are known in the art, for instance as described in “Crystalline polymorphism of organic compounds” (Caira, Topics in Current Chemistry, Springer, Berlin, Germany, volume 198, pages 163-208). Yet, this does not mean that a particular polymorph screen is a routine procedure (“Facts and fictions about polymorphism” Aurora et al, Chem. Soc. Rev., 2015, 44, 8619- 8635). Also, for any compound it is not possible to predict how many different crystal forms can be prepared, nor to predict the properties of crystal forms (“Polymorphism - A Perspective”, Bernstein, Crystal Growth and Design Perspective, 2011 , 11 , 632-650).

[0013] A new racemic solid form of the compounds of formula (I) and its preparation have now been discovered, designated as Form III. The racemic crystalline form, Form III, according to the present invention presents an optimized handling and processing, especially on manufacturing scale.

[0014] More particularly, the crystalline polymorph Form III being stable at storage temperatures, it is not associated with crystal growth during storage, contrary to Form RAC. Therefore, agrochemical compositions which comprise compound of formula (l-R) and compound of formula (l-S) are stable over storage when the racemic solid form is present as Form III, together with solid Form A of the most abundant enantiomer.

[0015] Examples of such agrochemical compositions are agrochemical compositions containing Feneptamidoquin in the form of a combination of solid Form A of compound of formula (l-R) (pure enantiomer solid form) and the racemic solid form designated as Form III.

[0016] More particularly, the crystalline Form III is a racemate, meaning that it contains compound of formula (l-R) and compound of formula (l-S) in equal proportions. The racemic solid Form III may be characterized by a powder X-ray diffraction pattern expressed in terms of 20 angles and / or d spacings.

[0017] The crystalline Form III of compound of formula (l-R) and (l-S) can have a powder X-ray diffraction pattern comprising at least three 20 angle values, preferably at least six 20 angle values, preferably at least eight 20 angle values, and more preferably at least ten 20 angle values, selected from the group consisting of 8.0 ± 0.2°, 8.4 ± 0.2°, 10.0 ± 0.2°, 10.6 ± 0.2°, 10.8 ± 0.2°, 11.9 ± 0.2°, 13.2 ± 0.2°, 14.2 ± 0.2°, 15.2 ± 0.2°, 15.3 ± 0.2°, 16.0 ± 0.2°, 16.5 ± 0.2°, 17.0 ± 0.2°, 17.6 ± 0.2°, and 17.9 ± 0.2°.

[0018] In a preferred embodiment, the crystalline Form III of compound of formula (l-R) and (l-S) can have a powder X-ray diffraction pattern comprising two, three or all of 20 angle values selected from the group consisting of 8.0 ± 0.2°, 13.2 ± 0.2°, 15.2 ± 0.2°, 16.0 ± 0.2°. Preferably, the crystalline Form III of compound of formula (l-R) and (l-S) can have a powder X- ray diffraction pattern comprising two, three or all of 20 angle values selected from the group consisting of 8.0 ± 0.2°, 13.2 ± 0.2°, 15.2 ± 0.2°, 16.0 ± 0.2°; and at least one 20 angle value, preferably at least two 20 angle values, preferably at least four 20 angle values, more preferably at least six 20 angle values, and even more preferably at least eight 20 angle values, selected from the group consisting of:

[0019] 8.4 ± 0.2°, 10.0 ± 0.2°, 10.6 ± 0.2°, 10.8 ± 0.2°, 11.9 ± 0.2°, 14.2 ± 0.2°, 15.3 ± 0.2°, 16.5 ± 0.2°, 17.0 ± 0.2°, 17.6 ± 0.2°, and 17.9 ± 0.2°.

[0020] In another preferred embodiment, the crystalline Form III of compound of formula (l-R) and (I- S) can have a powder X-ray diffraction pattern comprising the 20 angle values: 8.0 ± 0.2°, 13.2 ± 0.2°,

[0021] 15.2 ± 0.2°, 16.0 ± 0.2°; at least one 20 angle value, preferably at least two 20 angle values, preferably at least four 20 angle values, more preferably at least six 20 angle values, and even more preferably at least eight 20 angle values, selected from the group consisting of: 8.4 ± 0.2°, 10.0 ± 0.2°, 10.6 ± 0.2°, 10.8 ± 0.2°, 11.9 ± 0.2°, 14.2 ± 0.2°, 15.3 ± 0.2°, 16.5 ± 0.2°, 17.0 ± 0.2°, 17.6 ± 0.2°, and 17.9 ± 0.2°.

[0022] For instance, the crystalline Form III of compound of formula (l-R) and (l-S) can have a powder X-ray diffraction pattern comprising two, three or all of 20 angle values, preferably three or all of 20 angle values, selected from the group consisting of 8.0 ± 0.2°, 13.2 ± 0.2°, 15.2 ± 0.2°, 16.0 ± 0.2°; and at least one 20 angle value, preferably at least two 20 angle values, preferably at least four 20 angle values, more preferably at least six 20 angle values, and even more preferably at least eight 20 angle values, selected from the group consisting of: 8.4 ± 0.2°, 10.0 ± 0.2°, 10.6 ± 0.2°, 10.8 ± 0.2°, 11.9 ± 0.2°,

[0023] 14.2 ± 0.2°, 15.3 ± 0.2°, 16.5 ± 0.2°, and 17.0 ± 0.2°.

[0024] In an embodiment, the racemic crystalline Form III of compound of formula (I) can have a powder X-ray diffraction pattern comprising: two, three or four 20 angle values selected from the group consisting of: 8.0 ± 0.2°, 13.2 ± 0.2°,

[0025] 15.2 ± 0.2°, 16.0 ± 0.2°; at least one 20 angle value, preferably at least two 20 angle values, preferably at least four 20 angle values, more preferably at least six 20 angle values, and even more preferably at least eight 20 angle values, selected from the group consisting of: 8.4 ± 0.2°, 10.0 ± 0.2°, 10.6 ± 0.2°, 10.8 ± 0.2°, 11.9 ± 0.2°, 14.2 ± 0.2°, 15.3 ± 0.2°, 16.5 ± 0.2°, 17.0 ± 0.2°, 17.6 ± 0.2°, and 17.9 ± 0.2°; and at least one 20 angle value, preferably at least three 20 angle values, more preferably at least five 20 angle values, selected from the group consisting of: 4.0 ± 0.2°, 7.1 ± 0.2°, 7.5 ± 0.2°, 9.1 ± 0.2°,

[0026] 9.5 ± 0.2°, 11.6 ± 0.2°, 14.7 ± 0.2°, 18.8 ± 0.2°.

[0027] In an embodiment, the racemic crystalline Form III of compound of formula (I) can have a powder X-ray diffraction pattern comprising the 20 angle values: 8.0 ± 0.2°, 13.2 ± 0.2°, 15.2 ± 0.2°, 16.0 ± 0.2°; and 8.0 ± 0.2°; and at least two 20 angle values, preferably at least four 20 angle values, more preferably at least six 20 angle values, and even more preferably at least eight 20 angle values, selected from the group consisting of: 8.4 ± 0.2°, 10.0 ± 0.2°, 10.6 ± 0.2°, 10.8 ± 0.2°, 11.9 ± 0.2°, 14.2 ± 0.2°, 15.3 ± 0.2°,

[0028] 16.5 ± 0.2°, 17.0 ± 0.2°, 17.6 ± 0.2°, and 17.9 ± 0.2°.

[0029] In an embodiment, the racemic crystalline Form III of compound of formula (I) can have a powder X-ray diffraction pattern comprising the 20 angle values: 8.0 ± 0.2°, 13.2 ± 0.2°, 15.2 ± 0.2°, 16.0 ± 0.2°; and 8.0 ± 0.2°; and at least six 20 angle values, such as eight 20 angle values, or all 20 angle values, selected from the group consisting of: 8.4 ±0.2°, 10.0 ±0.2°, 10.6 ±0.2°, 10.8 ±0.2°, 11.9 ±0.2°,

[0030] 14.2 ± 0.2°, 15.3 ± 0.2°, 16.5 ± 0.2°, 17.0 ± 0.2°, 17.6 ± 0.2°, and 17.9 ± 0.2°.

[0031] In another embodiment, the racemic crystalline Form III can have a powder X-ray diffraction pattern comprising the 20 angle values: 8.0 ± 0.2°, 8.4 ± 0.2°, 10.0 ±0.2°, 10.6 ±0.2°, 10.8 ±0.2°, 11.9 ±0.2°, 13.2 ±0.2°, 14.2 ±0.2°, 15.2 ±0.2°, 15.3 ±0.2°, 16.0 ±0.2°, 16.5 ±0.2°, 17.0 ±0.2°, 17.6 ±0.2°, and 17.9 ±0.2°.

[0032] More particularly, the crystalline Form III of compound of formula (I) can have a powder X-ray diffraction pattern comprising at least the following 20 angle values: 8.0 ± 0.2°, 10.0 ±0.2°,

[0033] 13.2 ± 0.2°, 17.9 ± 0.2°, 21.0 ±0.2°,; preferably at least the following 20 angle values: of 4.0 ± 0.2°, 7.1 ±0.2°, 8.0±0.2°, 8.4 ± 0.2°, 9.1 ±0.2°, 10.0±0.2°, 10.6±0.2°, 11.6±0.2°, 13.2±0.2°,

[0034] 14.2 ±0.2°, 15.2 ±0.2°, 16.0 ±0.2°, 16.5 ±0.2°, 17.0 ±0.2°, 17.9 ±0.2°, 18.8 ±0.2°, 19.2 ±0.2°, 19.7±0.2°, 20.1 ±0.2°, 21.0±0.2°, 24.5±0.2°, 26.9 ± 0.2°, 27.3 ± 0.2°, 27.8 ± 0.2°, 30.4±0.2°,

[0035] 38.4 ±0.2°. and more preferably at least the following 20 angle values: 4.0 ± 0.2°, 7.1 ± 0.2°, 8.0 ± 0.2°,

[0036] 8.4 ± 0.2°, 9.1 ±0.2°, 10.0±0.2°, 10.6±0.2°, 11.6±0.2°, 13.2±0.2°, 14.2±0.2°, 15.2±0.2°, 16.0 ±0.2°, 16.5 ±0.2°, 17.0 ±0.2°, 17.9 ±0.2°, 18.8 ±0.2°, 19.2 ±0.2°, 19.7 ±0.2°, 20.1 ±0.2°, 21.0 ± 0.2°, 24.5 ± 0.2°, 26.9 ± 0.2°, 27.3 ± 0.2°, 27.8 ± 0.2°, 30.4 ± 0.2°, 38.4 ± 0.2°.

[0037] For instance, the crystalline Form III of compound of formula (l-R) and (l-S) has a powder X-ray diffraction pattern comprising all 20 angle values selected from the group consisting of 4.0 ± 0.2°, 7.1 ±0.2°, 8.0±0.2°, 8.4 ± 0.2°, 9.1 ±0.2°, 10.0±0.2°, 10.6±0.2°, 11.6±0.2°, 13.2±0.2°,

[0038] 14.2 ±0.2°, 15.2 ±0.2°, 16.0 ±0.2°, 16.5 ±0.2°, 17.0 ±0.2°, 17.9 ±0.2°, 18.8 ±0.2°, 19.2 ±0.2°, 19.7±0.2°, 20.1 ±0.2°, 21.0±0.2°, 24.5±0.2°, 26.9 ± 0.2°, 27.3 ± 0.2°, 27.8 ± 0.2°, 30.4±0.2°,

[0039] 38.4 ±0.2°.

[0040] These peak values, along with the corresponding d spacing values are shown in Table 1 below.

[0041] Table 1

[0042] W= Weak, M= Medium, S= Strong

[0043] These 20 angle values are derived from a powder X-ray diffraction pattern of the racemic solid form of formula (I) designated as Form III obtained using the method of Example 3. The values are generated using an average wavelength of 1 .54056A with a 20 step size of 0.02°. The crystalline polymorph (Form III) of the invention may also be characterized by the unit cell parameters of its single crystal as shown in Table 2. The racemic crystalline Form III was obtained using the methods described in Example 3.

[0044] Table 2

[0045] In Table 2, a, b, c are the lengths of the edges of the unit cell; a, p, y are the angles of the unit cell.

[0046] In a particular embodiment of the present invention, the crystalline polymorph can have the following lattice parameters: a=11.8 ± 0.1 A, b=15.2 A ± 0.1 A, c=44.1 A ± 0.1 A, a = 90°, p = 97± 0.2°, y = 90°, and volume = 7870 ± 138A3.

[0047] In another embodiment, the crystalline polymorph according to the invention can have a melting point ranging from 99 to 105°C (peak position), and preferably ranging from 101 to 103°C (peak position). This melting point is obtained using Differential Scanning Calorimetry (DSC) with a heating rate of 10 °C / minute.

[0048] The crystalline polymorph designated Form III may also be characterized by a Raman spectra expressed in terms of Raman shift (cm'1). Thus, in another embodiment of the invention, the crystalline polymorph has a Raman spectra comprising at least three, at least six, at least nine, at least twelve, at least fifteen, or all Raman shift values selected from the group consisting of:

[0049] 1663 ±2 cm1, 1626 ±2 cm1, 1602 ±2 cm1, 1572 ±2 cm1, 1527 ±2 cm1, 1494 ±2 cm1, 1470 ±2 cm1, 1444 ±2 cm1, 1407 ±2 cm1, 1371 ±2 cm1, 1350 ±2 cm1, 1292 ±2 cm1,

[0050] 1249 ±2 cm1, 1203 ±2 cm1, 1192 ±2 cm1, 1156 ±2 cm1, 1078 ±2 cm1, 1045 ±2 cm1,

[0051] 1029±2cnr1, 1000±2cnr1, 971 ±2cm1, 951 ±2cm1, 921 ±2cm1, 891 ±2cm1, 873±2cnr1, 851 ±2 cm1, 780 ±2 cm1, 738 ±2 cm1, 710 ±2 cm1, 618 ±2 cm1, 559 ±2 cm1, 492 ±2 cm1,

[0052] 477 ± 2 cm1, 451 ± 2 cm1, 432 ± 2 cm1, 345 ± 2 cm1, 271 ± 2 cm1236 ± 2 cm1.

[0053] In the context of the present invention, a polymorph is a particular crystal form of a chemical compound that can exist in more than one crystal form in the solid state. A crystal form of a compound contains the constituent molecules arranged in orderly repeating patterns extending in all three spatial dimensions (in contrast, an amorphous solid form has no long-range order in the position of molecules). Different polymorphs of a compound have different arrangements of atoms and or molecules in their crystal structure. When the compound is a biologically active compound, such as a fungicide, the difference in crystal structures can lead to different polymorphs having different chemical, physical and biological properties. Properties which may be affected include crystal shape, density, hardness, colour, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. As such, a specific polymorph may have properties which make it more advantageous in a particular use relative to another polymorph of the same compound: in particular, the physical, chemical and biological properties listed above can have a significant effect on the development of production methods, especially at manufacturing scale, and on formulations; on the ease with which a compound can be combined in a formulation with other active ingredients and formulation components; and / or on the quality and efficacy of plant treatment agents, such as fungicides. It is noted that predicting whether the solid state of a compound may be present as more than one polymorph is not possible and nor is it possible to predict the properties of any of these crystal forms.

[0054] In particular, use of a specific polymorph may allow use of new formulations compared with existing polymorphic / amorphous forms of a compound. This might be advantageous for a number of reasons. For example, a suspension concentrate (SC) formulation may be preferred over an emulsion concentrate (EC) because the lack of solvent in the suspension concentrate may mean that the SC formulation is likely to be less phytotoxic than an equivalent EC formulation. However, if the existing form of a compound is not stable in such an SC formulation, polymorphic conversion might occur leading to unwanted crystal growth. Such crystal growth is detrimental because it may lead to, for example, thickening of the formulation, and even potentially to solidification of the formulation. A direct consequence may be blockage in application equipment, e.g. in spray nozzles in agricultural application machinery. Using a stable polymorphic form would overcome these issues.

[0055] Assaying the solid phase for the presence of crystals may be carried out by conventional methods known in the art. For example, it is convenient and routine to use powder X-ray diffraction techniques. Other techniques which may be used include differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Raman spectroscopy, near infra-red spectroscopy, mid infra-red spectroscopy, nuclear magnetic resonance (NMR), gas chromatography or high-performance liquid chromatography (HPLC). Single crystal X-ray diffraction is especially useful in identifying crystal structures.

[0056] Another object of the present invention relates to a method of preparing the crystalline polymorph (Form III), comprising the following steps:

[0057] (i) mixing the compounds l-R and l-S (50:50), with a mixed organic solvent, to obtain a slurry of compounds l-R and l-S, and

[0058] (ii) stirring the slurry of compounds l-R and l-S at a temperature ranging from 5 °C to 50 °C for up to 5 days, and

[0059] (iii) harvesting crystals as they form.

[0060] In step (i), the solvent system may be a mix of water and ethanol. For instance, the solvent system is 60% water in ethanol.

[0061] Preferably, step (ii) is performed at a temperature ranging from 5 °C to 50 °C, such as less than 30 °C, and more preferably at a temperature of 5 °C up to 25 °C. Step (ii) can be advantageously performed under constant stirring, and more preferably under constant mild stirring. Step (ii) may last up to five days, preferably up to three days, and more preferably at least two days. The inventors believe that the higher the stirring temperature, the shorter the time needed to harvest racemic crystalline Form III.

[0062] The step (iii) may take the form of a filtering step of the suspension, in order to isolate the crystals generated in the step (ii) from their solvent(s).

[0063] The crystals Form III may be used as solid seeds, which may help reducing the time required to obtain racemic crystalline Form III.

[0064] The polymorphs of the invention may be applied in unchanged form but are more preferably incorporated into an agrochemical composition by conventional means. Accordingly, a further object according to the invention relates to an agrochemical composition comprising the crystalline polymorph as defined in the present invention, and at least one an agriculturally acceptable carrier or diluent. The agrochemical composition comprising the crystalline polymorph of the present invention can be used for the control of plant pathogenic fungi on a number of plant species.

[0065] In addition, compositions of the invention may comprise more than one polymorph of compound of formula (I). In particular, the compound of formula l-R is more biologically active than the compounds of formula l-S. As such, whilst the compositions ofthe invention may contain a mixture of the compounds l-R and l-S in the polymorphic forms disclosed herein or otherwise in any amounts, they may also be enriched for the compound of formula l-R or a polymorph of the compound of formula l-R. In particular, they may be enriched for the polymorph designated Form A. “Enriched” means that the molar proportion of the compound or polymorph of formula l-R compared to the total amount of the compounds of formula l-R and l-S is greater than 50%, e.g, at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98 or at least 99%. Preferably, the molar proportion of the compound or polymorph of formula l-R compared to the total amount of the compounds of formula l-R and l-S is greater than 90%, more preferably greater than 95%, such as, greater than 98%.

[0066] When compound of formula (l-R) and compound of formula (l-S) are both present in a composition, the least abundant enantiomer may be found as racemic solid Form III together with the most abundant enantiomer, and the remainder of the most abundant enantiomer may be found as a pure enantiomer Form A. As an example, if a composition contains compound (l-R) and compound (I- S) in a ratio l-R / l-S of 90:10, the composition may contain 80mol% of Form A and 20mol% of Form III. As compound of formula (l-S) and compound of formula (l-R) have the same molecular weight, the ratio l-R I l-S may be viewed as a molar ratio as well as a weight ratio. Other examples are given in Table A below:

[0067] Table A

[0068] In compositions that contain both enantiomers (l-R) and (l-S), it is preferable that the pure enantiomer solid Form A be present together with the racemic solid Form III, rather than with the conglomerate solid Form RAC. The reason is, as will be shown in the examples, that the solid Form RAC does not seem to be stable over storage: crystal growth has been observed during storage in some formulations. This uncontrolled crystal growth is not desired. However, racemic solid Form III remains stable to crystal growth over storage.

[0069] Therefore, an object of the present invention relates to a composition comprising compound of formula (l-R) in a content of CR weight % and compound of formula (l-S) in a content of Cs weight %, wherein CR ranges from 80 to 99.9% of C + Cs and wherein compounds of formula (l-R) and of formula (l-S) are present as the racemic crystalline Form III in a content of about 2 x Cs, and as an enantiomerically pure solid form of compound (l-R), such as Form A, in a content of about CR - CS. As CR may range from 80% to 99.9% of CR + Cs, by construction, Cs ranges from 0.1 % to 20% of CR + Cs.

[0070] Examples of weight ratio CR I Cs are given in Table A. For instance, the weight ratio CR I Cs ranges from 80 : 20 to 99.9 : 0.1 , such as from 80 : 20 to 99.5 : 0.5, from 90 : 10 to 98 : 5, or from 90 : 10 to 95 : 5.

[0071] As compound of formula (l-R) is more active than compound of formula (l-S), it is desirable that CR be higher than Cs. However, reaching a 100% enantiomeric purity is difficult to achieve in an industrial setting. Therefore it is acceptable that the composition contains a small amount of compound of formula (l-S).

[0072] Should compound (l-S) prove to have specific activity, it may become interesting to invert the CR I Cs ratio, or even to use a racemic compound of formula (I). In this case, a composition comprising compound of formula (l-R) and compound of formula (l-S), in a content CR and Cs respectively, wherein Cs I CR ranges from 50:50 to 99.9:0.1 , wherein racemic solid Form III represents about 2 x CR of the composition, and solid form A of compound (l-S) represents about Cs - CR of the composition.

[0073] Preferably, an object of the present invention relates to a composition containing N-[(1 RS)-1 ,3- dimethyl-1-(phenylmethyl)butyl)]-8-fluoro-3-quinolinecarboxamide (i.e. compound of formula I), up to about 20 wt% of which being the S-enantiomer (preferably from about 0.1 wt% to about 20 wt%), wherein up to about 40 wt% of compound of formula I is in the form of a racemic solid form (preferably from about 0.2 wt% to about 40 wt%), in particular as racemic solid form III, and at least about 60 wt% of compound of formula I is in the form of solid form A (i.e. the pure enantiomer solid form of compound of formula l-R of example 1) (preferably from about 60 wt% to about 99.8 wt%). Various weight or molar ratios are given in Table A above.

[0074] Another object of the present invention is agrochemical composition comprising compound of formula (I) wherein compound of formula (I) is comprised of at least about 80 wt% of compound of formula (l-R) and of up to about 20 wt% of compound of formula (l-S) and wherein up to about 40% of compound of formula (I) is in the form of a racemic solid form, preferably of racemic solid Form III. Preferably, compound of formula (I) is comprised of from about 80 wt% to about 99.9 wt% of compound of formula (l-R) and from about 0.1 wt% to about 20 wt% of compound of formula (l-S), and wherein from about 0.20 wt% to about 40 wt% of compound of formula (I) is in the form of the racemic solid Form III. Most preferably from about 60 wt% to about 99.8 wt% of compound of formula (I) is in the form of solid Form A. Various weight or molar ratios are given in Table A above.

[0075] Also preferably, the agrochemical composition is a suspension concentrate.

[0076] Another object of the present invention relates to a method of preventing or controlling fungal infection on plants or plant propagation material comprising treating the plant or plant propagation material with said agrochemical composition, and preferably with a fungicidally effective amount of said agrochemical composition.

[0077] The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. The term "plant propagation material" is understood to denote all the generative parts of the plant, such as seeds, which can be used for the multiplication of the latter including vegetative plant material such as cuttings. There may be mentioned, as plant propagation material, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, or parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. The plant propagation material can be treated with the composition of the invention before the material is sown or planted. Alternatively, the plant propagation material may be treated with the composition of the invention during sowing or planting. Additionally, the composition of the invention may be applied to the previously treated propagation material before orduring its planting. The composition ofthe invention may be applied during the sowing of the seed. The composition may also be used to plant propagation material derived from plants grown in a green house and / or during transplantation.

[0078] More preferably the plant propagation material is plant seeds. The seed treatment can occur to an unsown seed, and the term "unsown seed" is meant to include seed at any period between the harvest of the seed and the sowing of the seed in the ground for the purpose of germination and growth of the plant. Treatment to an unsown seed is not meant to include those practices in which the composition is applied to the soil but would include any application practice that would target the seed during the sowing / planting process. The treated plant propagation material of the present invention can be treated in the same manner as conventional plant propagation material. The treated propagation material can be stored, handled, sown and tilled in the same manner as any other pesticide treated material.

[0079] The agrochemical composition of the invention can be used to control, for example, Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula, Corynespora, Phyllachora); Fungi imperfecti (also known as Deuteromycetes; e.g. Botrytis, Helminthosporium, Fusarium, Cercospora, Altemaria and Pyricularia).

[0080] The agrochemical composition of the present invention is suitable for controlling such disease on a number of plants and their propagation material including, but not limited to the following target crops: cereals (wheat, barley, rye, oats, maize (including field corn, pop corn and sweet corn), rice, sorghum and related crops); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, sunflowers); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); vegetables (spinach, lettuce, asparagus, cabbages, eggplants, onions, pepper, tomatoes, potatoes,); plantation crops (bananas, fruit trees,), ornamentals (flowers, shrubs,); as well as other plants such as vines, bushberries (such as blueberries), caneberries, cranberries, and turf grasses including, but not limited to, cool-season turf grasses (for example, bluegrasses (Poa L.), such as Kentucky bluegrass (Poa pratensis L.), rough bluegrass (Poa trivialis L.), Canada bluegrass (Poa compressa L.) and annual bluegrass (Poa annua L.); bentgrasses (Agrostis L.), such as creeping bentgrass (Agrostis palustris Huds.), colonial bentgrass (Agrostis tenius Sibth.), velvet bentgrass (Agrostis canina L.) and redtop (Agrostis alba L.); fescues (Festuca L.), such as tall fescue (Festuca arundinacea Schreb.), meadow fescue (Festuca elatiorL.) and fine fescues such as creeping red fescue (Festuca rubra L.), chewings fescue (Festuca rubra var. commutata Gaud.), sheep fescue (Festuca ovina L.) and hard fescue (Festuca longifolia); and ryegrasses (Lolium L.), such as perennial ryegrass (Lolium perenne L.) and annual (Italian) ryegrass (Lolium multiflorum Lam.)) and warm-season turf grasses, for example, Bermuda grasses (Cynodon L. C. Rich), including hybrid and common Bermudagrass; Zoysiagrasses (Zoysia Willd .), St. Augustine grass (Stenotaphrum secundatum (Walt.) Kuntze); and centipedegrass (Eremochloa ophiuroides (Munro.) Hack.).

[0081] In addition ‘crops’ are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola. Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

[0082] Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include 8-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.

[0083] An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0084] In particular, the composition according to the invention is particularly effective against leafspot species; early blights and molds; especially against Fusarium in cereals; Sclerotinia in vegetables and oil seed rape; grey mold in vine; Botrytis cinerea, Monilinia spp. and Venturia spp. in fruits; and Phyllachora maydis in corn.

[0085] Therefore, the invention also relates to the use of Form III of compound of formula (I) (compounds l-R and l-S), or of a composition containing it, to prevent or control a fungal infection on plants, in particular to prevent or control fungal infection caused by Fusarium spp. in cereals, such as wheat, barley, oat, or rye; to prevent or control fungal infection caused by Sclerotinia in vegetables, or in oil seed rape; to prevent or control grey mold in vine; to prevent or control fungal infection caused by Botrytis cinerea, Monilinia spp. or Venturia spp., in fruits; and to prevent or control fungal infection caused by Phyllachora maydis in corn.

[0086] The composition according to the invention is furthermore particularly effective against seedborne and soilborne diseases, such as Botrytis cinerea, Cercospora spp., Colletotrichum spp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusarium subglutinans, Pyricularia oryzae, Sclerotinia spp., in particular against pathogens of cereals, such as wheat, barley, rye or oats; maize; rice; turf; and oil seed rape. The composition according to the invention is furthermore particularly effective against post harvest diseases such as Botrytis cinerea, Colletotrichum musae, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, in particular against pathogens of fruits, such as pomefruits, for example apples and pears, stone fruits, for example peaches and plums, and berries, for example strawberries,

[0087] The composition according to the invention is particularly useful for controlling the following diseases on the following crops: Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes, such as Botrytis cinerea on grape; Colletotrichum species in fruit and vegetables, such as Colletotrichum acutatum in strawberries ; Fusarium species in cereals Mycosphaerella fijiensis in banana; Pyricularia oryzae in rice; Sclerotinia species in lawns, lettuce, vegetables and oil seed rape, such as Sclerotinia sclerotiorum on oilseed rape Venturia species in fruits, such as Venturia inequalis on apple; and Monilinia species on fruits.

[0088] The rate at which the agrochemical composition of the invention is applied will depend upon the particular type of fungus to be controlled, the degree of control requed and the timing and method of application and can be readily determined by the person skilled in the art. In general, the composition of the invention can be applied at an application rate of between 0.005 kilograms / hectare (kg / ha) and about 5.0 kg / ha, based on the total amount of active fungicide in the composition. An application rate of between about 0.1 kg / ha and about 1 .5 kg / ha is preferred, with an application rate of between about 0.3 kg / ha and 0.8 kg / ha being especially preferred.

[0089] In preferred embodiments, the agrochemical composition comprises a molar ratio of compound l-R I compound l-S of at least 80:20, preferably at least 90:10. It may be applied at a rate of about 100 g to 200 g of active ingredient (i.e. compound l-R plus compound l-S) per hectare, to target the pathogens listed in Table B below:

[0090] Table B

[0091] In practice, the agrochemical composition comprising the polymorphs of the invention is applied as a formulation containing the various adjuvants and carriers known to or used in the industry. They may thus be formulated as granules, as wettable powders, as emulsifiable concentrates, as suspension concentrates (including oil dispersions), as powders or dusts, as flowables, as solutions, as suspensions or emulsions, suspo-emulsions or as controlled release forms such as microcapsules. Suitably, the agrochemical composition of the invention may be formulated as a suspension concentrate, a suspo- emulsion, an emulsion concentrate or a wet granulation. These formulations are described in more detail below and may contain as little as about 0.5% to as much as about 95% or more by weight of the active ingredient in the form of the polymorph. The optimum amount will depend on formulation, application equipment and nature of the plant pathogenic fungi to be controlled.

[0092] Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain by weight about 5% to about 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.

[0093] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient by weight may range from about 0.5% to about 95% of the concentrate.

[0094] Suspension concentrates are formulations in which finely divided solid particles of the active compound are stably suspended. The solid particles may be suspended in an aqueous solution or in an oil (as an oil dispersion). Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient by weight may range from about 0.5% to about 95% of the concentrate. Granular formulations include both extrudates and relatively coarse particles and may be applied without dilution to the area in which control of plant pathogenic fungi is required or dispersed in a spray tank before application, for example. Typical carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations for use without dilution normally contain by weight about 5% to about 25% active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and / or stickers such as dextrins, glue or synthetic resins. When the granules are to be dispersed in a spray tank before application, the active ingredient content by weight may be increased up to 80%.

[0095] Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.

[0096] Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically from about 1 to about 50 microns in diameter. The enclosed liquid typically constitutes about 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre (and preferably from 1 to 2 millimetres) in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrenebutadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

[0097] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.

[0098] Many of the formulations described above include wetting, dispersing or emulsifying agents. Examples are alkyl and alkylaryl sulphonates and sulphates and their salts, polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines. These agents, when used, normally comprise from 0.1 % to 40% by weight of the formulation.

[0099] Suitable agricultural adjuvants and carriers that are useful in formulating the composition of the invention in the formulation types described above are well known to those skilled in the art. Suitable examples of the different classes are found in the non-limiting list below.

[0100] Liquid carriers that can be employed include water and any solvents in which the polymorph has no or limited solubility e.g. toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 ,1 ,1- trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulphonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerine, N- methyl-2-pyrrolidinone, and the like. Water is generally the carrier of choice for the dilution of concentrates.

[0101] Suitable solid carriers include talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin and the like.

[0102] A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. The surfaceactive agents can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface-active agents include salts of alkyl sulphates, such as diethanolammonium lauryl sulphate; alkylarylsulphonate salts, such as calcium dodecylbenzenesulphonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol- C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulphonate salts, such as sodium dibutylnaphthalenesulphonate; dialkyl esters of sulphosuccinate salts, such as sodium di(2- ethylhexyl) sulphosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.

[0103] Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants, sticking agents, and the like. Each of the above formulations can be prepared as a package containing the fungicides together with other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.). The formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.

[0104] These formulations can be applied to the areas where control is desired by conventional methods. Dust and liquid compositions, for example, can be applied by the use of power-dusters, broom and hand sprayers and spray dusters. The formulations can also be applied from airplanes as a dust or a spray or by rope wick applications. Both solid and liquid formulations may also be applied to the soil in the locus of the plant to be treated allowing the active ingredient to penetrate the plant through the roots. The formulations of the invention may also be used for dressing applications on plant propagation material to provide protection against fungus infections on the plant propagation material as well as against phytopathogenic fungi occurring in the soil. Suitably, the active ingredient may be applied to plant propagation material to be protected by impregnating the plant propagation material, in particular, seeds, either with a liquid formulation of the fungicide or coating it with a solid formulation. In special cases, other types of application are also possible, for example, the specific treatment of plant cuttings or twigs serving propagation.

[0105] Suitably, the agrochemical compositions and formulations of the present invention are applied prior to disease development. Rates and frequency of use of the formulations are those conventionally used in the art and will depend on the risk of infestation by the fungal pathogen.

[0106] The compositions and formulations of the present invention can also be used in combination with other active ingredients, e.g. other fungicides, and / or insecticides, and / or acaricides, and / or nematocides, and / or molluscicides, and / or biologicals, and / or plant growth regulators. Such mixtures, and the use of such mixtures to control weeds and / or undesired plant growth form yet further aspects of the invention.

[0107] In a preferred embodiment, the agrochemical composition can comprise at least one further fungicide, and optionally can further comprise at least one insecticide and / or at least one nematicide.

[0108] When the crystalline polymorph of the invention is combined with at least one additional fungicide, the following fungicidal mixing partners are preferred:

[0109] - a strobilurin fungicide selected from the group consisting of azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin;

[0110] - an azole fungicide selected from the group consisting of azaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate, penconazole, prochloraz, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, diclobutrazol, etaconazole, furconazole, furconazole-cis and quinconazole;

[0111] - a morpholine fungicide selected from the group consisting of aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine and piperalin;

[0112] - an anilino-pyrimidine fungicide selected from the group consisting of cyprodinil, mepanipyrim and pyrimethanil; and / or - a fungicide selected from the group consisting of benalaxyl, benalaxyl-M, benomyl, bitertanol, boscalid, captan, carboxin, carpropamid, chlorothalonil, copper, cyazofamid, cymoxanil, diethofencarb, dithianon, famoxadone, fenamidone, fenhexamide, fenoxycarb, fenpiclonil, fluazinam, fludioxonil, flutolanil, folpet, guazatine, hymexazole, iprodione, lufenuron, mancozeb, metalaxyl, mefenoxam, metrafenone, nuarimol, paclobutrazol, pencycuron, penthiopyrad, procymidone, proquinazid, pyroquilon, quinoxyfen, silthiofam, sulfur, thiabendazole, thiram, triazoxide, tricyclazole, isopyrazam, sedaxane, fluxapyroxad, benzovindiflupyr and 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2- (2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide.

[0113] Whilst compositions comprising the polymorph of the invention and another fungicide are explicitly disclosed above, the skilled person will appreciate that the invention extends to three-way, and further multiple combinations comprising the above two-way mixtures.

[0114] For the avoidance of doubt, even if not explicitly stated above, the mixing partners of may also be in the form of any suitable agrochemically acceptable ester or salt, as mentioned e.g. in The Pesticide Manual, Nineteenth Edition, British Crop Protection Council 2021.

[0115] BRIEF DESCRIPTION OF THE DRAWINGS

[0116] The present invention will now be described by way of the following non-limiting examples and figures, wherein:

[0117] FIG. 1 shows the powder X-ray diffraction pattern of the crystalline polymorph (Form A). Legend: x-axis: 20 angle (°); y-axis: count

[0118] FIG. 2 shows the X-ray diffraction pattern calculated from the unit cell parameters according to Table 2, of the crystalline polymorph (Form A). Legend: x-axis: 20 angle (°); y-axis: count.

[0119] FIG. 3 shows a DSC trace of the crystalline polymorph (Form A). Legend: x-axis: temperature (°C); y-axis: normalised heat flow (W / g).

[0120] FIG. 4 shows a IR spectroscopy trace of the crystalline polymorph (Form A). Legend x-axis: wavenumbers (cm'1); y-axis: transmittance (%).

[0121] FIG. 5 shows a DSC trace of the racemic mixture (Form RAC). Legend: x-axis: temperature (°C); y-axis: normalised heat flow (W / g).

[0122] FIG. 6 shows the powder X-ray diffraction pattern of the crystalline polymorph (Form III) according to the present invention. Legend: x-axis: 20 angle (°); y-axis: count

[0123] FIG. 7 shows the X-ray diffraction pattern calculated from the unit cell parameters according to Table 2, of the crystalline polymorph (Form III) according to the present invention. Legend: x-axis: 20 angle (°); y-axis: count.

[0124] FIG. 8 shows a DSC trace of the crystalline polymorph (Form III) according to the present invention. Legend: x-axis: temperature (°C); y-axis: normalised heat flow (W / g).

[0125] FIG. 9 shows a spectroscopy trace of the crystalline polymorph (Form III) according to the present invention. Legend x-axis: wavenumbers (cm1); y-axis: absorbance (counts).

[0126] FIG. 10 shows the particle size distribution of the samples SC1 (fig. 10A) and SC2 (fig 10B) before and after the various storage conditions described above. Legend for Figure 10 (logarithmic scale): Initial = thin solid line; after storage A = dotted lined; after storage B = dashed line; after storage C = dotted / dashed line; after storage D = bold solid line. FIG. 11 and 12 show optical micrographs of SC1 and SC2, respectively, after storage (example 4). Figure 11 A: SC1 after storage condition A; 11 B: SC1 after storage condition B; 11 C: SC1 after storage condition C. Figure 12A: SC2 before storage; 12B: SC2 after storage condition D.

[0127] EXAMPLES

[0128] Example 1 - Form A of compound of formula l-R

[0129] 1 . Preparation of the polymorph

[0130] The compound of formula (l-R) (0.08g) was dissolved in ethyl acetate (1 mL) at room temperature (about 20°C). The solution was left to evaporate for at least 16 hours. Any crystals formed were harvested and analysed by powder X-ray diffraction (pXRD), differential scanning calorimetry (DSC) and I R spectroscopy.

[0131] 2. Analysis of the polymorph

[0132] After preparation by the method detailed above, the samples were subject to analysis by powder X-ray diffraction, and / or single crystal X-ray diffraction, and / or differential scanning calorimetry, and / or near infra-red spectroscopy, and / or mid infra-red spectroscopy.

[0133] Powder X-ray diffraction analysis of solid material was carried out using a Malvern Panalytical Empyrean powder diffractometer at room temperature (20 °C) and at relative humidities above 40%. Samples were mounted in a standard PMMA sample holders and the samples flattened. The sample holder was rotated, and X-rays were collected from 3.5 to 40° 20 with a step size of 0.02° and incident x-rays with wavelength of 1.5406 A. The powder X-ray diffraction pattern of the crystalline polymorph (Form A) according to the invention is shown in FIG. 1 .

[0134] Single crystal intensity data was collected on an Rigaku Supernova diffractometer using Cu Ka radiation (a=1 .54056 A) with a graphite monochromator. The crystal was mounted in NVH oil at -173 °C for data collection. The data was solved using the CRYSTALS software package, and the results are gathered in Table 2 (unit cell parameters). The X-ray diffraction pattern calculated from the unit cell parameters of the crystalline polymorph (Form A) is shown in FIG. 2.

[0135] DSC was carried out using a TA DSC2500, using standard 40 pL aluminium sample holders with pierced lids (to allow the escape of any gas formed during the heating of the sample), heating from 25 to 200 °C at a rate of 10 °C / minute. The DSC trace of the crystalline polymorph (Form A) according to the invention is shown in FIG. 3. The peak temperature is about 146°C with an onset at about 144°C.

[0136] Infra-red (IR) analysis was carried out using a Thermo Scientific™ Nicolet iS5 FT-IR Spectrometer with an iD7 ATR attachment. The analysis was performed using a scan range of 500- 4000 cm-1with 16 repeat scans. A background scan was measured with no sample present, before adding 1-10mg of sample to cell. The IR spectroscopy trace of the crystalline polymorph (Form A) is shown in FIG. 4.

[0137] 3. Results of the analysis of Form A

[0138] Powder X-ray diffraction - Peak values along with the corresponding d spacing values are shown in Table A-1 below:

[0139] Table A-1

[0140] W= Weak, M= Medium, S= Strong

[0141] Unit cell parameters - The unit cell parameters of a single crystal A as shown in Table A-2. Table A-2

[0142] In Table 2, a, b, c are the lengths of the edges of the unit cell; and a, p, y are the angles of the unit cell.

[0143] Infra-red (IR) analysis - IR spectra of crystalline polymorph Form A 3246 ±2 cm1, 3077 ±2 cm1, 3030 ±2 cm1, 2983 ±2 cm1, 2960 ±2 cm1, 2946 ±2 cm1,

[0144] 2925 ±2 cm1, 2866 ±2 cm1, 1629 ±2 cm1, 1608 ±2 cm1, 1560 ±2 cm1, 1495 ±2 cm1,

[0145] 1466±2cnr1, 1451 ±2cm1, 1415±2cm1, 1374 ±2cm1, 1343±2cnr1, 1318±2cnr1,

[0146] 1300 ±2 cm1, 1280 ±2 cm1, 1248 ±2 cm1, 1220 ±2 cm1, 1199 ±2 cm1, 1163 ±2 cm1,

[0147] 1142 ±2 cm1, 1101 ±2 cm1, 1076 ±2 cm1, 1044 ±2 cm1, 986 ±2 cm1, 959 ±2 cm1, 944 ±2 cm1, 927 ± 2 cm1, 875 ± 2 cm1, 825 ± 2 cm1, 781 ± 2 cm1, 749 ± 2 cm1, 740 ± 2 cm1, 701 ± 2 cm1, 648 ± 2 cm1, 633 ± 2 cm1, 623 ± 2 cm1, 606 ± 2 cm1, 581 ± 2 cm1, 564 ± 2 cm1and 543 ± 2 cm1.

[0148] A solid form of compound of formula l-S may also be prepared as outlined in this example 1 , starting from compound of formula l-S instead of compound of formula l-R. Different enantiomers have the same physical properties so they will have the same polymorphs.

[0149] Example 2 - Form RAC of racemate of compound of formula (I)

[0150] 1. Preparation of Form RAC

[0151] RAC form was prepared by dissolving equal masses of the compound of formula l-R and l-S in ethyl acetate, the solvent was then allowed to evaporate for at least 16 hours. The resulting solid was analysed by DSC.

[0152] 2. Analysis of Form RAC

[0153] DSC was carried out using a TA DSC2500, using standard 40 pL aluminium sample holders with pierced lids (to allow the escape of any gas formed during the heating of the sample), heating from 25 to 200 °C at a rate of 1 °C / minute. The DSC trace of the racemic mixture (Form RAC) according to the invention is shown in FIG.5. The peak temperature is about 113°C with an onset at about 111 °C.

[0154] 3. Results of the analysis

[0155] The crystalline polymorph Form RAC can have a melting point ranging from 110 to 115 °C (peak position), such as from 111 to 113 °C (peak position). This melting point is obtained using Differential Scanning Calorimetry (DSC) with a heating rate of 1 °C / minute.

[0156] Example 3 - Racemic solid Form III of compound of formula (I)

[0157] 1. Preparation of the polymorph

[0158] Equal masses of the compound of formula l-R and l-S (0.2g) was suspended in 60% water: ethanol (1 mL) at room temperature (about 20°C). The solution was left to stir for a maximum of 3 days. Any crystals formed were harvested and analysed by powder X-ray diffraction (pXRD), differential scanning calorimetry (DSC) and Raman spectroscopy.

[0159] 2. Analysis of the polymorph

[0160] After preparation by the method detailed above, the samples were subject to analysis by powder X-ray diffraction, and / or single crystal X-ray diffraction, and / or differential scanning calorimetry, and / or near infra-red spectroscopy, and / or mid infra-red spectroscopy. Powder X-ray diffraction analysis of solid material was carried out using a Malvern Panalytical Empyrean powder diffractometer at room temperature (20 °C) and at relative humidities above 40%. Samples were mounted in a standard PMMA sample holders and the samples flattened. The sample holder was rotated, and X-rays were collected from 3.5 to 40° 20 with a step size of 0.02° and incident x-rays with wavelength of 1.5406 A. The powder X-ray diffraction pattern of the crystalline polymorph (Form III) according to the invention is shown in FIG.6. Detailed data is outlined in Table 1 above.

[0161] Single crystal intensity data was collected on an Rigaku Supernova diffractometer using Cu Ka radiation (a=1.54056 A) with a graphite monochromator. The crystal was mounted in NVH oil at -173 °C for data collection. The data was solved using the CRYSTALS software package, and the results are gathered in Table 2 (unit cell parameters). The X-ray diffraction pattern calculated from the unit cell parameters of the crystalline polymorph (Form III) is shown in FIG.7. Detailed data is outlined in Table 2 above.

[0162] DSC analysis was carried out using the Mettler Toledo DSC1 using standard 40 pL aluminium sample holders with pierced lids (to allow the escape of any gas formed during the heating of the sample), heating from 25 to 250°C at a heating rate of 10°C / min. The DSC trace of the crystalline polymorph (Form III) according to the invention is shown in FIG.8. The peak temperature is about 102°C with an onset at about 100°C.

[0163] The Raman spectra was collected using a Thermo DXR Raman microscope instrument with

[0164] 780nm excitation laser. The laser power was set to 10 mW and the samples exposed for 1sec for 25 repeats. 1 mg of sample was placed on a quartz slide. The Raman spectroscopy trace of the crystalline polymorph (Form III) is shown in FIG.9. Measured Raman shift values:

[0165] 1663 ±2 cm1, 1626 ±2 cm1, 1602 ±2 cm1, 1572 ±2 cm1, 1527 ±2 cm1, 1494 ±2 cm1,

[0166] 1470 ±2 cm1, 1444 ±2 cm1, 1407 ±2 cm1, 1371 ±2 cm1, 1350 ±2 cm1, 1292 ±2 cm1,

[0167] 1249 ±2 cm1, 1203 ±2 cm1, 1192 ±2 cm1, 1156 ±2 cm1, 1078 ±2 cm1, 1045 ±2 cm1,

[0168] 1029 ±2cm-1, 1000 ±2cm-1, 971 ±2cm1, 951 ±2cm1, 921 ±2cm1, 891 ±2cm1, 873 ±2cnr1, 851 ±2 cm1, 780 ±2 cm1, 738 ±2 cm1, 710 ±2 cm1, 618 ±2 cm1, 559 ±2 cm1, 492 ±2 cm1,

[0169] 477 ± 2 cm1, 451 ± 2 cm1, 432 ± 2 cm1, 345 ± 2 cm1, 271 ± 2 cm1236 ± 2 cm1.

[0170] Example 4 - Formulation stability

[0171] Two suspension concentrate formulations (SC) were prepared containing 10%w / w of active ingredient, one as Form RAC and the other as Form III. The preparation of solid Form RAC is outlined in example 2. The preparation of racemic crystalline Form III is outlined in example 3.

[0172] Each SC was divided and stored under three different controlled storage conditions as explained in Table 3 below:

[0173] Table 3 Storage conditions are as follows:

[0174] A - 4 weeks at 40°C

[0175] B - 4 weeks cycling at 10°C for 12 hours and then 40°C for 12 hours followed by an additional 100 weeks at ambient conditions (about 20°C)

[0176] C - 4 weeks at 40°C followed by an additional 100 weeks at ambient conditions (about 20°C)

[0177] D - 8 weeks cycling at 10°C for 12 hours and then 40°C for 12 hours

[0178] A typical suspension concentrate formulation is given in Table 4 below:

[0179] Table 4

[0180] The particle size distribution was measured at the beginning of storage and after each storage condition. The measurement was performed via static laser diffraction using a Malvern Mastersizer 3000 with a Hydro MV automatic liquid sample dispersion unit. A sample of SC was diluted into water within the dispersion unit until an appropriate obscuration was achieved, at which point the median volume distribution (d(50)) was calculated for each sample via MIE theory calculation. The d(50) results are shown in Table 5 below.

[0181] Table 5

[0182] Figure 10 shows the particle size distribution of the samples SC1 (fig. 10A) and SC2 (fig 10B) before and after the various storage conditions described above. Legend for Figure 10 (logarithmic scale):

[0183] Initial = thin solid line; after storage A = dotted lined; after storage B = dashed line; after storage C = dotted / dashed line; after storage D = bold solid line.

[0184] As can be seen with the peak shift, formulation SC1 , which contains only racemic Form RAC, undergoes crystal growth during storage throughout the sample. On the other hand, formulation SC2 which contains racemic Form III, does not undergo crystal growth during storage.

[0185] The samples were also analysed via optical light microscopy after storage, the results of which can be found in Figures 11 and 12.

[0186] Fig. 11 A = SC1 after storage condition A Fig. 11B = SC1 after storage condition B

[0187] Fig. 11C = SC1 after storage condition C

[0188] Fig. 12A = SC2 before storage

[0189] Fig. 12B = SC2 after storage condition D This shows that large crystals form during storage of the formulation SC1 , which contains only

[0190] Form RAC. SC2 which contains Form III does not undergo crystal growth during storage.

Claims

CLAIMS1 . A racemic crystalline form of the compound of formula Iwhich has a powder X-ray diffraction pattern comprising at least three 20 angle values selected from the group consisting of 8.0 ± 0.2°, 8.4 ± 0.2°, 10.0 ± 0.2°, 10.6 ± 0.2°, 10.8 ± 0.2°, 1 1.9 ± 0.2°, 13.2 ± 0.2°, 14.2 ± 0.2°, 15.2 ± 0.2°, 15.3 ± 0.2°, 16.0 ± 0.2°, 16.5 ± 0.2°, 17.0 ± 0.2°, 17.6 ± 0.2°, and 17.9 ± 0.2°.

2. The racemic crystalline form according to claim 1 , characterized in that the powder X-ray diffraction pattern comprises two, three or all of the 20 angle values selected from the group consisting of: 8.0 ± 0.2°, 13.2 ± 0.2°, 15.2 ± 0.2°, 16.0 ± 0.2°; and at least one 20 angle value selected from the group consisting of: 8.4 ± 0.2°, 10.0 ± 0.2°, 10.6 ± 0.2°, 10.8 ± 0.2°, 11.9 ± 0.2°, 14.2 ± 0.2°, 15.3 ± 0.2°, 16.5 ± 0.2°, and 17.0 ± 0.2°.

3. The racemic crystalline form according to claim 1 or claim 2, characterized in that the powder X-ray diffraction pattern comprises at least the following 20 angle values: 8.0 ± 0.2°, 13.2 ± 0.2°, 15.2 ± 0.2°, 16.0 ± 0.2.

4. The racemic crystalline form according to any one of the preceding claims, characterized in that it has the following lattice parameters:

5. The racemic crystalline form according to any one of the preceding claims, characterized in that it has a melting point ranging from 99 to 105°C (peak position), and preferably ranging from 101 to 103°C (peak position).

6. An agrochemical composition comprising the racemic crystalline form as claimed in any one of claims 1 to 5, and at least one agriculturally acceptable carrier or diluent.

7. The composition according to claim 6, characterised in that it comprises compound of formula (l-R) in a content of CR weight % and compound of formula (l-S) in a content of Cs weight %, wherein CR ranges from 80 to 99.9% of CR + Cs, and wherein compounds of formula (l-R) and of formula (l-S) are present as the racemic crystalline form according to any one of claims 1 to 5, in a content of about 2 x Cs, and as an enantiomerically pure solid form of compound (l-R), in a content of about CR - Cs.

8. An agrochemical composition comprising compound of formula (I)wherein compound of formula (I) is comprised of at least 80 wt% of compound of formula (l-R) and of up to 20 wt% of compound of formula (l-S):and wherein up to 40% of compound of formula (I) is in the form of the racemic solid form according to any one of claims 1 to 5.

9. The composition according to claim 8, wherein compound of formula (I) is comprised of from 80 wt% to 99.9 wt% of compound of formula (l-R) and from 0.1 wt% to 20 wt% of compound of formula (l-S), and wherein from 0.20 wt% to 40 wt% of compound of formula (I) is in the form of the racemic solid form according to any one of claims 1 to 5.

10. The composition according to any of claims 6 to 9, characterized in that it comprises at least one further fungicide.11 . The composition according to any one of claims 6 to 10, characterized in that the at least one further fungicide is a strobilurin or an azole.

12. The composition according to any one of claims 6 to 11 , characterized in that it further comprises at least one insecticide and / or at least one nematicide.

13. The composition according to any one of claims 6 to 12, which is a suspension concentrate.

14. A method of preventing or controlling fungal infection on plants or plant propagation material comprising treating the plant or plant propagation material with the agrochemical composition as claimed in any one of claims 6 to 13.

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