Solid state forms of cyantraniliprole and uses thereof

Abstract

The present invention relates to new solid forms of brofenprox, to processes for their preparation, to their uses and to agrochemical compositions thereof.

Description

Technical Field

[0001] This disclosure relates to a novel solid form of cyantraniliprole, its preparation method, and its agrochemical compositions. The invention also relates to a method for preparing crystalline forms of cyantraniliprole from the aforementioned novel form. Background Technology

[0002] Controlling invertebrate pests is crucial for achieving high crop efficiency. Damage to agronomically grown and stored crops by invertebrate pests can lead to significant yield reductions and consequently increased costs for consumers. Certain o-aminobenzamides, their N-oxides, salts, and compositions are suitable for both agronomic and non-agronomic uses, as well as methods for controlling invertebrate pests in both agronomic and non-agronomic environments. Controlling invertebrate pests in forestry, greenhouse crops, ornamental plants, nursery crops, stored food and fiber products, livestock, households, and public and animal health is also important.

[0003] Bromnipotent is a ryanoid anthranilamide insecticide. It is a systemic diamide insecticide specifically designed to control lepidopteran pests in agriculture. It is a promising insecticide due to its unique mode of action in activating ryanoid receptors in muscle, leading to contraction and paralysis in some pests. It has been registered for use against lepidopteran pests and aphids on several fruits and vegetables, including apples, peaches, tomatoes, watermelons, and cucumbers.

[0004] Bromnipotent has the chemical name 3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-1H-pyrazole-5-carboxamide.

[0005] Bromnipotent has the following chemical structure:

[0006]

[0007] Bromnipotent, its N-oxide or salt, and methods thereof were first disclosed by DuPont in international publication WO 2004 / 067528. Further methods for its preparation are disclosed in WO 2006 / 062978 and WO 2010 / 056720. WO 2006 / 062978 discloses a purification method for bromnipotent by recrystallization of the crude product from 1-propanol.

[0008] Furthermore, WO 2010056720 discloses a method for preparing a non-hydrated polymorph A of broflanilide from a hydrated polymorph B of broflanilide. More specifically, WO 2010056720 relates to a method for preparing polymorph A of broflanilide, which involves heating a mixture containing a solvent and polymorph B of broflanilide at a temperature between about 40°C and the boiling point of a solvent, wherein the solvent is selected from the group consisting of water, n-heptane, 1-chlorobutane, toluene, 1-butanol, and 1-pentanol. A disadvantage of the method for preparing polymorph A of broflanilide in WO 2010056720 is that it requires heating and / or crystallization. Therefore, there is a need for a method for preparing polymorph A of broflanilide that does not require any heating or any kind of crystallization.

[0009] In addition, WO 2021 / 249395 also discloses other crystal forms of bromocyanamide (such as form C, form D and form F) and their preparation methods.

[0010] Polymorphism, the phenomenon of different crystal forms, is a characteristic of some molecules and molecular complexes. A single compound, like bromocyanamide, can produce multiple polymorphs with different crystal structures and physical properties. These physical properties include melting point, thermal behavior (e.g., measured by thermogravimetric analysis – "TGA" or differential scanning calorimetry – "DSC"), X-ray powder diffraction (XRPD) patterns, infrared absorption fingerprints, Raman absorption fingerprints, and solid-state properties. 13 C-NMR spectroscopy. One or more of these techniques can be used to distinguish different polymorphic forms of compounds.

[0011] Different salts and solid forms (including solvated forms) of active ingredients can have different properties. This variation in the properties of different salts and solid forms and solvates can provide a basis for improving formulations, for example, by facilitating better processing or handling characteristics, improving solubility profiles, or improving stability (polymorphism and chemical stability) and shelf life. These variations in the properties of different salts and solid forms can also provide improvements to the final formulation or formulation, for example, if they are used to improve solubility. Different salts and solid forms and solvates of active ingredients can also produce a variety of polymorphs or crystal forms, which in turn provides additional opportunities to provide improved products using variations in the properties and characteristics of solid active ingredients.

[0012] Inventing new salts, solid forms, and solvates of agrochemical products can provide materials with desired processing properties (such as ease of handling, processability, storage stability, and ease of purification) or serve as desirable intermediate crystal forms that facilitate conversion to other salts or polymorphic forms. New salts, polymorphic forms, and solvates of active ingredients can also provide opportunities to improve the performance characteristics (solution profiles, permeability, etc.) of agrochemical products. This expands the range of materials that those skilled in the art can use for formulation optimization, for example, by providing products with different properties, such as different crystal habits, higher crystallinity, or polymorphic stability, which can provide better processing or handling characteristics, improved solubility profiles, or improved shelf life.

[0013] The search for new solid forms and solvates also facilitates the preparation of other forms of active ingredients. The interconversion of one form of an active ingredient to another opens up new and useful options in this field.

[0014] For at least these reasons, there is a need for some novel solid forms of bromocyanamide (including solvated forms or salts). Summary of the Invention

[0015] This disclosure relates to a new solid form of bromocyanamide, its preparation method, and agricultural chemical compositions comprising this solid form.

[0016] This disclosure also relates to a method for preparing crystalline forms of broflanilide from the aforementioned novel form of broflanilide.

[0017] This disclosure also provides the use of one solid form of cyantraniliprole for the preparation of other solid forms of cyantraniliprole, cyantraniliprole N-oxide, and cyantraniliprole salts in solid form.

[0018] In the embodiments, this disclosure provides the use of bromethrin form O for the preparation of bromethrin form A.

[0019] In another embodiment, this disclosure provides the use of bromethrin form W for the preparation of bromethrin form A.

[0020] In another embodiment, this disclosure provides the use of cyantraniliprole form Z for the preparation of cyantraniliprole form A.

[0021] This disclosure also provides solid forms of cyantraniliprole, other solid forms used to prepare cyantraniliprole, cyantraniliprole N-oxides, and cyantraniliprole salts in solid forms.

[0022] In one embodiment, this disclosure covers the solid form of the described bromocyanamide for the preparation of agrochemical compositions and / or formulations optionally for agronomic and non-agronomic uses, and methods thereof for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0023] In another embodiment, this disclosure covers the use of the described bromocyanamide in solid form for the preparation of agricultural chemical compositions and / or formulations.

[0024] This disclosure further provides agricultural chemical compositions comprising one or more bromocyanamides in solid form according to this disclosure.

[0025] In yet another embodiment, this disclosure covers agricultural chemical formulations comprising one or more of the described bromocyanamide in solid form and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and optionally in an effective amount of at least one additional bioactive compound or reagent.

[0026] This disclosure covers a method for preparing the agrochemical formulation of bromocyanamide, the agrochemical formulation comprising one or more of the described solid forms and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and optionally an effective amount of at least one additional bioactive compound or reagent.

[0027] Agricultural chemical compositions or formulations in the solid form as defined herein, as well as in the solid form of bromocyanamide, can be used as systemic diamide insecticides for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0028] This disclosure also provides methods for controlling invertebrate pests by applying a solid form of bromocyanamide to activate muscle lanyl alkaloid receptors, thereby causing some pests to contract and become paralyzed.

[0029] This disclosure also provides the use of the solid form of bromocyanamide or at least one of the above-described agrochemical compositions or formulations for the control of invertebrate pests in both agronomic and non-agronomic environments. Attached Figure Description

[0030] Figure 1 The X-ray powder diffraction (XRPD) pattern of bromocyanamide in form O is shown.

[0031] Figure 2 The X-ray powder diffraction (XRPD) pattern of bromocyanamide in form W is shown.

[0032] Figure 3The X-ray powder diffraction (XRPD) pattern of form Z of bromocyanamide is shown. Detailed Implementation

[0033] This disclosure relates to the solid form of cyantraniliprole, its preparation method, and agricultural chemical compositions comprising the solid form. This disclosure also relates to converting the described solid form of cyantraniliprole into other solid forms of cyantraniliprole, cyantraniliprole N-oxides, cyantraniliprole salts, and their solid forms.

[0034] According to this disclosure, the solid form of bromocyanamide may have advantageous properties selected from at least one of the following: chemical or polymorphic purity, fluidity, solubility, dissolution rate, morphology or crystal habit, stability (such as chemical stability with respect to polymorphic transformation, as well as thermal and mechanical stability, dehydration stability and / or storage stability), low degree of hygroscopicity, low residual solvent content, and advantageous processing and handling characteristics (such as compressibility or bulk density).

[0035] The crystalline form characteristics mentioned herein can be found in the graphical data illustrated in the figures. Such data includes, for example, powder X-ray diffraction patterns and solid-state NMR spectra. As is well known in the art, graphical data can potentially provide additional technical information to further define the corresponding solid-state form, which need not be described by reference to individual numerical values ​​or peak positions. In any case, those skilled in the art will understand that the graphical representation of these data may vary slightly due to factors well known to them, such as variations in instrument response and variations in sample concentration and purity, for example, variations in relative peak intensities and peak positions. Nevertheless, those skilled in the art will be able to readily compare the graphical data in the figures herein with graphical data generated from unknown crystalline forms and confirm whether the two sets of graphical data represent the same crystalline form or characteristics of two different crystalline forms. Therefore, the crystalline form of bromocyanamide characterized by the graphical data “illustrated in the figures” mentioned herein will be understood to include any crystalline form of bromocyanamide characterized by such small changes in its graphical data compared to the figures, as is well known to those skilled in the art.

[0036] The term "pure solid form" (or "polymorph") may be referred to herein as "polymorphically pure" or "substantially free of any other solid (or polymorph) form." As used herein, in this context, the expression "substantially free of any other form" will be understood to mean that the solid form contains about 20% or less, about 10% or less, about 5% or less, about 2% or less, about 1% or less, or 0% of any other form of the subject compound, as measured, for example, by XRPD. Therefore, the solid form of cyantraniliprole described herein as substantially free of any other solid form should be understood to contain greater than about 80% (w / w), greater than about 90% (w / w), greater than about 95% (w / w), greater than about 98% (w / w), greater than about 99% (w / w), or 100% of the subject solid form of cyantraniliprole. Therefore, in some embodiments disclosed herein, the solid form of the described bromocyanamide may contain about 1% to about 20% (w / w), about 5% to about 20%, or about 5% to about 10% (w / w) of one or more other solid forms of the same bromocyanamide.

[0037] In one aspect, this disclosure takes into account that a certain solid form of cyantraniliprole can exist in the presence of any other solid form or mixture thereof. Therefore, in one embodiment, this disclosure provides form A, for example, wherein form A is present in a solid form comprising less than 95%, less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, less than 3%, or less than 1% by weight of any other physical form of cyantraniliprole.

[0038] The solid form of bromocyanamide, as characterized herein, can also be present in trace amounts in agrochemical compositions or formulations used to control invertebrate pests in both agronomic and non-agronomic environments.

[0039] As used herein, unless otherwise specified, the XRPD peaks reported herein may optionally use CuK. α The radiation was measured at λ = 1.54187 Å.

[0040] As used herein, the term “isolated” in relation to the solid form of cyantraniliprole disclosed herein refers to the solid form of cyantraniliprole physically isolated from the reaction mixture in which cyantraniliprole is formed.

[0041] A substance, such as a reaction mixture, may be described herein as being at or permitted to reach “room temperature” (often abbreviated as “RT”). This means that the temperature of the substance is close to or the same as the temperature of the space in which the substance is located (e.g., a room or fume hood). Typically, room temperature is from about 20°C to about 30°C, from about 22°C to about 27°C, or about 25°C.

[0042] The process or step may be referred to as “overnight” in this document. This refers to a time interval, for example, for a process or step, that spans the time during the night, during which the process or step may not be actively observed. This time interval is from about 8 to about 20 hours, about 10 to about 18 hours, or about 16 hours.

[0043] The amount of solvent used in a chemical process (such as a reaction or crystallization) may be referred to herein as a quantity in “vol” or “V”. For example, a material may be described as being suspended in 10 volumes (or 10 vol or 10 V) of solvent. In this context, the expression will be understood to mean the number of milliliters of solvent per gram of suspended material; therefore, suspending 5 grams of material in 10 volumes of solvent means that the amount of solvent used per gram of suspended material is 10 milliliters, or in this example, 50 mL of solvent. In another context, the term “v / v” may be used to indicate the volume of solvent added to a liquid mixture based on the volume of the mixture. For example, adding methyl tert-butyl ether (MTBE) (1.5 v / v) to 100 mL of a reaction mixture will indicate that 150 mL of MTBE has been added.

[0044] As used in this article, the term "decompression" refers to a pressure of about 10 millibars to about 50 millibars.

[0045] This disclosure includes the solid form of broflanilide designated as form O. Form O of broflanilide can be data characterized by one or more of the following: XRPD plots with peaks at 7.5, 8.3, 13.1, 14.9, and 21.1 degrees 2-θ ± 0.2 degrees 2-θ; as in... Figure 1 The XRPD diagram shown in the figure; and combinations of these data.

[0046] The crystal form O of bromocyanamide can be further characterized by an XRPD plot having peaks at 7.5, 8.3, 13.1, 14.9, and 21.1 degrees 2-θ ± 0.2 degrees 2-θ, and also having one, two, or three additional peaks selected from 18.5, 19.5, 19.8, 20.2, and 24.1 degrees 2-θ ± 0.2 degrees 2-θ.

[0047] The crystal form O of bromocyanamide can be characterized as follows: Figure 1 Any combination of at least four peaks in the XRPD plot shown.

[0048] In the examples, the crystal form O of bromocyanamide is a 1,4-dioxane solvate.

[0049] This disclosure also includes the solid form of broflanilide designated as form W. Form W of broflanilide can be characterized by data selected from one or more of the following: XRPD plots with peaks at 6.6, 9.7, 17.6, 20.2, and 21.1 degrees 2-θ ± 0.2 degrees 2-θ; as in... Figure 2 The XRPD diagram shown in the figure; and combinations of these data.

[0050] The crystal form W of bromocyanamide can be further characterized by an XRPD plot having peaks at 6.6, 9.7, 17.6, 20.2, and 21.1 degrees 2-θ ± 0.2 degrees 2-θ, and also having one, two, or three additional peaks selected from 10.7, 14.9, 15.8, 18.6, and 27.1 degrees 2-θ ± 0.2 degrees 2-θ.

[0051] The crystal form W of bromocyanamide can be characterized as follows: Figure 2 Any combination of at least four peaks in the XRPD plot shown.

[0052] In the examples, the crystal form W of bromocyanamide is a solvate.

[0053] This disclosure further includes the solid form of broflanilide designated as form Z. Form Z of broflanilide can be data characterized by one or more of the following: XRPD plots with peaks at 8.6, 9.0, 15.6, 17.2, and 23.0 degrees 2-θ ± 0.2 degrees 2-θ; as in Figure 3 The XRPD diagram shown in the figure; and combinations of these data.

[0054] The crystal form Z of bromocyanamide can be further characterized by an XRPD plot having peaks at 8.6, 9.0, 15.6, 17.2, and 23.0 degrees 2-θ ± 0.2 degrees 2-θ, and also having one, two, or three additional peaks selected from 10.5, 11.3, 19.3, 20.2, 21.1, and 24.1 degrees 2-θ ± 0.2 degrees 2-θ.

[0055] The crystal form Z of bromocyanamide can be characterized as follows: Figure 3 Any combination of at least four peaks in the XRPD plot shown.

[0056] In the examples, the crystal form Z of bromocyanamide is anhydrous.

[0057] In another embodiment, this disclosure provides a method for preparing crystalline form O of bromocyanamide, the method comprising slurrying bromocyanamide form B with 1,4-dioxane, followed by filtration and drying.

[0058] In the embodiments, this disclosure provides a method for preparing crystalline form W of bromocyanamide, the method comprising dissolving bromocyanamide form B in a chlorinated hydrocarbon solvent, mixing it with an aliphatic hydrocarbon solvent, and then stirring, filtering and drying.

[0059] In a specific embodiment, this disclosure provides a method for preparing crystalline form W of bromocyanamide, the method comprising dissolving bromocyanamide form B in dichloromethane, mixing with n-heptane, and then stirring, filtering and drying.

[0060] In an embodiment, this disclosure provides a method for preparing crystalline form Z of bromocyanamide, the method comprising heating bromocyanamide form F at a high temperature overnight.

[0061] In the embodiments, this disclosure provides a method for preparing crystalline form A of bromocyanamide, the method comprising starting from bromocyanamide in form O, slurrying it with a suitable solvent selected from 1-propanol, 1-butanol, n-heptane, methylcyclohexane, isoamyl alcohol, isobutanol, 1-pentanol, 2-butanol, isobutyl acetate, isobutyric acid, and isopropanol, and then decanting.

[0062] In another embodiment, this disclosure provides a method for preparing crystalline form A of bromocyanamide, the method comprising starting from bromocyanamide in form W, slurrying it with a suitable solvent selected from 1-propanol, 1-butanol, 1-pentanol, n-heptane, methylcyclohexane, isoamyl alcohol, isobutanol, 2-butanol, isobutyl acetate, isobutyric acid, and isopropanol, and then decanting.

[0063] In another embodiment, this disclosure provides a method for preparing crystalline form A of bromocyanamide, the method comprising starting from bromocyanamide in form F, slurrying it with a suitable solvent selected from 1-propanol, 1-butanol, 1-ethanol, n-heptane, methylcyclohexane, isoamyl alcohol, isobutanol, 1-pentanol, 2-butanol, isobutyl acetate, isobutyric acid, and isopropanol, and then decanting.

[0064] In another embodiment, this disclosure provides a method for preparing crystalline form A of broflanilide, the method comprising starting from the amorphous form of broflanilide, slurrying it with a suitable solvent selected from 1-propanol, 1-butanol, 1-ethanol, n-heptane, methylcyclohexane, isoamyl alcohol, isobutanol, 1-pentanol, 2-butanol, isobutyl acetate, isobutyric acid, and isopropanol, and then decanting.

[0065] In a specific embodiment, this disclosure provides a method for preparing pure crystalline form A of bromocyanamide, the method comprising starting from a form of bromocyanamide selected from the group consisting of form O, form W, form F and amorphous forms.

[0066] In a more specific embodiment, this disclosure provides a method for preparing pure crystalline form A of bromocyanamide, the method comprising starting from form W.

[0067] In the embodiments, this disclosure provides a method for preparing amorphous bromocyanamide, the method comprising dissolving bromocyanamide form A in a chlorinated hydrocarbon solvent, mixing it with an aliphatic hydrocarbon solvent, and then stirring, filtering and drying.

[0068] In a specific embodiment, this disclosure provides a method for preparing amorphous bromocyanamide, the method comprising dissolving bromocyanamide form A in 1,1,2,2-tetrachloroethane, mixing with n-heptane, and then stirring, filtering and drying.

[0069] In the embodiments, this disclosure provides a method for preparing form F of bromocyanamide, the method comprising slurrying form O of bromocyanamide with an aromatic solvent, followed by filtration and drying.

[0070] In a specific embodiment, this disclosure provides a method for preparing form F of bromocyanamide, the method comprising slurrying form O of bromocyanamide with toluene, followed by filtration and drying.

[0071] This disclosure also provides the solid form of cyantraniliprole disclosed herein, other solid forms used to prepare cyantraniliprole, cyantraniliprole N-oxides, cyantraniliprole salts and their solid forms.

[0072] In another embodiment, this disclosure covers the solid form of bromocyanamide described above for use in the preparation of agrochemical compositions and / or formulations for optional agronomic and non-agronomic uses, and methods thereof for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0073] In another embodiment, this disclosure covers the use of the described bromocyanamide in solid form for the preparation of agricultural chemical compositions and / or formulations.

[0074] This disclosure further provides agricultural chemical compositions comprising one or more bromocyanamides in solid form according to this disclosure.

[0075] In yet another embodiment, this disclosure covers agricultural chemical formulations comprising one or more of the described bromocyanamide in solid form and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and optionally in an effective amount of at least one additional bioactive compound or reagent.

[0076] In the embodiments, this disclosure covers a method for preparing the agrochemical formulation of bromocyanamide, the agrochemical formulation comprising one or more of the described solid forms and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and optionally an effective amount of at least one additional bioactive compound or reagent.

[0077] In one embodiment, an agricultural chemical composition or formulation in the solid form as defined herein and in the solid form of bromocyanamide can be used as a systemic diamide insecticide for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0078] In another embodiment, this disclosure also covers methods for controlling invertebrate pests by administering a solid form of bromocyanamide to activate muscle lanyl base receptors, thereby causing some pests to contract and become paralyzed.

[0079] In yet another embodiment, this disclosure also covers the use of at least one of the solid form of bromocyanamide disclosed herein or the above-described agrochemical compositions or formulations for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0080] This disclosure has been described with reference to certain preferred embodiments, and other embodiments will become apparent to those skilled in the art upon consideration of the specification. This disclosure is further illustrated by reference to the following examples, which detail the methods for preparing and using the solid form of this disclosure. It will be apparent to those skilled in the art that many modifications can be made to both the materials and methods without departing from the scope of this disclosure.

[0081] Analytical methods

[0082] X-ray powder diffraction:

[0083] Powder X-ray diffraction was performed on a PANalytical AERIS X-ray powder diffractometer, which employed CuK... α Radiation (λ = 1.54060 Å-) operation; zero background sample holder.

[0084] Measurement parameters:

[0085] Scan range: 3 - 45 degrees 2-θ

[0086] Overall scan speed: 0.16098 0 / s

[0087] Sample holder: Zero background silicon substrate

[0088] Before analysis, the sample is gently ground into a fine powder using a mortar and pestle. Optionally, an appropriate amount of silica powder can be added as an internal standard to calibrate the diffraction positions. The ground sample is then placed into the chamber of the sample holder, and the sample surface is smoothed using the lid.

[0089] Example

[0090] The solid form of cyantraniliprole was prepared according to the following procedure:

[0091] Starting materials for preparing the solid form of the present invention are prepared according to existing technical procedures. For example, forms B and A of cyantraniliprole can be obtained by the procedures disclosed in WO 2006 / 062978 and also in WO 2010 / 056720. Form F of cyantraniliprole is disclosed by XRPD data in publication WO 2021 / 249395. Form F of cyantraniliprole can also be prepared according to WO 2021 / 249395 or the procedures described below. XRPD data for forms B and A are disclosed in WO 2010 / 056720.

[0092] New solid crystal forms of cyantraniliprole were prepared according to the following preparation examples:

[0093] Example 1: Preparation of form O of bromocyanamide:

[0094] 15 g of form B of bromocyanamide was weighed into a 250 mL glass bottle, and 150 mL of 1,4-dioxane was added. The solution was then kept on a magnetic stirrer for slurry preparation at room temperature (750 rpm for 18 hours). After 18 hours, the solution was filtered through Whatman filter paper, and XRPD studies were performed on the wet sample (decanted supernatant fraction) to confirm the formation of form O. Next, the sample was placed in vacuum drying for 3 hours (RT, 760 mmHg), and its XRPD was collected, showing that form O was retained after drying.

[0095] Example 1A: Preparation of form O of bromocyanamide (alternative method):

[0096] 150 g of bromocyanamide (form B) was stirred over a weekend in 1500 ml of 1,4-dioxane at room temperature, filtered, and air-dried. The solid was then gently ground with a spatula and analyzed by XRD.

[0097] Example 2: Preparation of cyantraniliprole in form W:

[0098] 1 g of bromocyanamide form B, along with large magnetic beads (size: 2 inches), was placed in a 2 L glass flask. 300 mL of DCM was added, and the mixture was kept on a magnetic stirrer and stirred for approximately 1 hour (RT, 650 rpm) until a clear solution was obtained. After the compound was completely dissolved in the DCM, 800 mL of n-heptane was added as quickly as possible, and the solution was stirred again for 4–5 minutes under the same reaction conditions. The solution was then filtered through Waterman (125 mm) filter paper. XRPD was performed on the grayish-white wet compound, which confirmed the formation of form W. The wet powder compound was then placed in a vacuum oven and dried at RT for approximately 3 hours. XRPD of the dried compound was then taken, indicating that form W was retained.

[0099] Example 3: Preparation of form Z of bromocyanamide:

[0100] A sample of 124 g of wet form F of cyantraniliprole (obtained by crystallization in toluene followed by filtration but without drying) was heated overnight at 150°C. The sample was then analyzed by XRPD.

[0101] Based on the following preparation examples, prepare known solid crystal form A of cyantraniliprole from other forms:

[0102] Example 4: Preparation of broflanilide form A from form F

[0103] Samples of form F of cyantraniliprole were placed individually in 7 mL glass vials, and the following solvents were added to the vials. The slurry was then stirred at room temperature (750 rpm) on a magnetic stirrer according to the following parameters. The solutions were then centrifuged at 7000 rpm (2 × 5 min) and subjected to XRPD studies (decanting the supernatant fraction) to confirm the formation of form A in each case.

[0104]

[0105] Obtain the pure form A of broflanilide under given conditions.

[0106] Example 5: Preparation of bromocyanamide form A from form O

[0107] Samples of form O were placed individually in 7 mL glass vials, and the following solvents were added to the vials. The slurry was then slurried at RT (750 rpm) on a magnetic stirrer according to the following parameters. The solutions were then centrifuged at 7000 rpm (2 × 5 min) and subjected to XRPD studies (decanting the supernatant fraction) to confirm the formation of form A in each case.

[0108]

[0109] Obtain the pure form A of broflanilide under given conditions.

[0110] Example 6: Preparation of bromocyanamide form A from form W

[0111] Samples of form W were placed individually in 7 mL glass vials, and the following solvents were added to the vials. The slurry was then slurried at RT (750 rpm) on a magnetic stirrer according to the following parameters. The solutions were then centrifuged at 7000 rpm (2 × 5 min) and subjected to XRPD studies (decanting the supernatant fraction) to confirm the formation of form A in each case.

[0112]

[0113] In all cases in the table above, bromocyanamide form A is obtained in its pure form.

[0114] Example 7: Preparation of bromocyanamide form A from amorphous slurry

[0115] The amorphous form of the sample was placed individually in a 7 mL glass vial, and the following solvent was added to the vial. The slurry was then slurried at RT (750 rpm) on a magnetic stirrer according to the following parameters. The solution was then centrifuged at 7000 rpm (2 × 5 min) and subjected to XRPD studies (decanting the supernatant fraction) to confirm the formation of form A in each case.

[0116]

[0117] Obtain the pure form A of broflanilide under given conditions.

[0118] The methods described in Examples 4-7 above also yielded pure form A. Purity was defined as the absence of any additional peaks detected in X-ray powder diffractometer. In terms of quantification, this corresponds to approximately 98% purity of form A.

[0119] Furthermore, based on the following preparation examples, the amorphous form and solid crystalline form F of cyanamide were prepared from other forms of cyanamide:

[0120] Example 8: Preparation of the amorphous form of bromocyanamide

[0121] Weigh 2 g of bromocyanamide form A and place it in a 100 mL glass bottle. Add 30 mL of 1,1,2,2-tetrachloroethane and stir the resulting mixture at 25°C (800 rpm) until a clear solution is obtained. Add 16 mL of n-heptane dropwise to the clear solution until a precipitate is observed. Slurry the resulting suspension at 25°C (800 rpm) for 20 min and filter the white suspension through Waterman (125 mm) filter paper. Dry the obtained solid under vacuum at 25°C (-760 mm Hg) for 18 h and collect PXRD data.

[0122] Example 9: Preparation of form F of bromocyanamide

[0123] Weigh 3.4 g of bromocyanamide form O and place it in a 100 mL glass bottle. Add 34 mL of toluene and slurry the resulting mixture at 25°C (800 rpm) for 18 hours. Filter the suspension through Waterman (125 mm) filter paper and collect PXRD data for the wet sample to confirm its form F.

Claims

1. A crystalline form O of bromocyanamide, characterized in that... Data selected from one or more of the following: i. XRPD plots showing peaks at 7.5, 8.3, 13.1, 14.9, and 21.1 degrees 2-θ ± 0.2 degrees 2-θ; ii. An XRPD diagram as shown in Figure 1.

2. The crystal form of bromocyanamide according to claim 1, characterized in that, Such an XRPD plot has peaks at 7.5, 8.3, 13.1, 14.9, and 21.1 degrees 2-θ ± 0.2 degrees 2-θ, and also has one, two, or three additional peaks selected from 18.5, 19.5, 19.8, 20.2, and 24.1 degrees 2-θ ± 0.2 degrees 2-θ.

3. The crystal form of bromocyanamide according to claim 1 is a 1,4-dioxane solvate.

4. A crystal form W of bromocyanamide, characterized in that... Data selected from one or more of the following: i. XRPD plots showing peaks at 6.6, 9.7, 17.6, 20.2, and 21.1 degrees 2-θ ± 0.2 degrees 2-θ; ii. The XRPD diagram as shown in Figure 2.

5. The crystal form of bromocyanamide according to claim 4, characterized in that, Such an XRPD plot has peaks at 6.6, 9.7, 17.6, 20.2, and 21.1 degrees 2-θ ± 0.2 degrees 2-θ, and also has one, two, or three additional peaks selected from 10.7, 14.9, 15.8, 18.6, and 27.1 degrees 2-θ ± 0.2 degrees 2-θ.

6. The crystal form of bromocyanamide according to claim 4 is a solvate.

7. A crystal form Z of bromocyanamide, characterized in that... Data selected from one or more of the following: i. XRPD plots showing peaks at 8.6, 9.0, 15.6, 17.2, and 23.0 degrees 2-θ ± 0.2 degrees 2-θ; ii. An XRPD diagram as shown in Figure 3.

8. The crystal form of bromocyanamide according to claim 7, characterized in that, Such an XRPD plot has peaks at 8.6, 9.0, 15.6, 17.2, and 23.0 degrees 2-θ ± 0.2 degrees 2-θ, and also has one, two, or three additional peaks selected from 10.5, 11.3, 19.3, 20.2, 21.1, and 24.1 degrees 2-θ ± 0.2 degrees 2-θ.

9. The crystal form of bromocyanamide according to claim 7, wherein it is anhydrous.

10. A method for preparing crystalline form O of bromocyanamide according to claim 1, the method comprising slurrying bromocyanamide form B with 1,4-dioxane, followed by filtration and drying.

11. A method for preparing crystalline form W of bromocyanamide according to claim 4, the method comprising dissolving bromocyanamide form B in a chlorinated hydrocarbon solvent, mixing it with an aliphatic hydrocarbon solvent, and then stirring, filtering and drying.

12. The method according to claim 11, wherein, The chlorinated hydrocarbon solvent is dichloromethane, and the aliphatic hydrocarbon solvent is n-heptane.

13. A method for preparing crystal form Z of bromocyanamide according to claim 7, the method comprising heating bromocyanamide form F at a high temperature overnight.

14. A method for preparing crystalline form A of broflanilide, the method comprising starting from the form of broflanilide and slurrying it with a suitable solvent selected from 1-propanol, 1-butanol, 1-pentanol, n-heptane, methylcyclohexane, isopentanol, isobutanol, 2-butanol, isobutyl acetate, isobutyric acid, and isopropanol.

15. The method according to claim 14, wherein, The starting form of bromocyanamide is selected from the group consisting of: form O, form W, form F and amorphous form.

16. The method according to any one of claims 14 and 15, wherein, The crystal form A of broflanilide is pure form A, which is prepared from broflanilide forms selected from the group consisting of: form O, form W, form F and amorphous form.

17. The method according to claim 16, wherein, The starting form of bromocyanamide is form W.

18. A method for preparing amorphous bromocyanamide, the method comprising dissolving bromocyanamide in form A in a chlorinated hydrocarbon solvent, mixing it with an aliphatic hydrocarbon solvent, and then stirring, filtering and drying.

19. The method according to claim 18, wherein, The chlorinated hydrocarbon solvent is 1,1,2,2-tetrachloroethane, and the aliphatic hydrocarbon solvent is n-heptane.

20. A method for preparing brofentanil form F, the method comprising slurrying brofentanil form O with an aromatic solvent, followed by filtration and drying.

21. The method according to claim 20, wherein, The aromatic solvent is toluene.

22. An agricultural chemical composition comprising the crystal form according to any one of claims 1-9.

23. Use of the crystal form according to any one of claims 1 to 9 in the preparation of agricultural chemical compositions and / or formulations.

24. An agricultural chemical formulation comprising a crystal form according to any one of claims 1-9 or an agricultural chemical composition according to claim 22, and at least one agriculturally acceptable excipient.

25. The agricultural chemical formulation according to claim 24, further comprising at least one surfactant, a solid diluent, a liquid diluent, or a combination thereof.

26. The crystal form according to any one of claims 1-9, the agricultural chemical composition according to claim 22, or the agricultural chemical formulation according to claim 24, for controlling invertebrate pests in both agronomic and non-agronomic environments.

27. Use of any one of the crystal forms according to any one of claims 1-9 for the preparation of any other crystal form of bromocyanamide.

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