Crystal form of acequinocyl and preparation method and application thereof

Abstract

The embodiment of the invention provides a crystal form of acequinocyl and a method for preparing the crystal form. The crystal form is a crystal form of acequinocyl shown as a formula I, Cu-K alpha radiation is used for # imgabs0 #, and an X-ray powder diffraction pattern of the crystal form has a characteristic peak at at least one position of a 2theta value of 3.3 degrees + / -0.2 degrees, 6.7 degrees + / -0.2 degrees, 10.4 degrees + / -0.2 degrees, 11.0 degrees + / -0.2 degrees, 13.5 degrees + / -0.2 degrees, 14.6 degrees + / -0.2 degrees, 17.1 degrees + / -0.2 degrees, 22.1 degrees + / -0.2 degrees or 24.5 degrees + / -0.2 degrees. A differential scanning calorimetry curve of the crystalline form obtained using a heating rate of 5 DEG C / min has at least one characteristic thermal event in the range of 55 DEG C to 60 DEG C. The acequinocyl crystal form has a higher melting point, a higher melting range starting temperature and a shorter melting range, and a water suspending agent prepared from the acequinocyl crystal form is not prone to phenomena such as creaming and the like, and is higher in quality, better in performance and longer in storage time.

Description

Technical Field

[0001] This specification relates to the field of acaricides, and particularly to the crystal form of acequinocyl, a method for preparing this crystal form, an agrochemical composition containing this crystal form, and a method for using this crystal form or this agrochemical composition to control agricultural pests. Background Art

[0002] Acequinocyl (2-(acetoxy)-3-dodecyl-1,4-naphthoquinone) is widely used internationally in acarid control in related fields such as agriculture and household due to its characteristics of high efficiency, low toxicity, broad spectrum, and biodegradability. However, the crystal form of commercially available acequinocyl currently has poor system compatibility and stability when preparing pesticide formulations, especially when preparing aqueous suspension concentrates, and is extremely prone to phenomena such as pasting and solidifying, resulting in serious product deterioration and inability to be used normally. The above situations greatly limit the application of acequinocyl aqueous suspension concentrates.

[0003] Therefore, it is necessary to provide a crystal form of acequinocyl and a method for preparing this crystal form to solve these problems. Summary of the Invention

[0004] One or more embodiments of this specification provide a crystal form of formula I acequinocyl. Formula I is Using Cu-Kα radiation, the X-ray powder diffraction (XRPD) pattern of this crystal form has characteristic peaks at least at one of the 2θ values of 3.3° ± 0.2°, 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2°, or 24.5 ± 0.2°; the differential scanning calorimetry (DSC) curve of this crystal form obtained at a heating rate of 5 °C / min has at least one characteristic thermal event in the range of 55 °C to 60 °C.

[0005] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form has a characteristic peak at a 2θ value of 3.3° ± 0.2°.

[0006] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form has a characteristic peak at a 2θ value of 3.3° ± 0.2°, and has characteristic peaks at least at two of 6.7° ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2°, or 24.5 ± 0.2°.

[0007] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form has a characteristic peak at a 2θ value of 3.3° ± 0.2°, and has characteristic peaks at at least three of 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2°, or 24.5 ± 0.2°.

[0008] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form has a characteristic peak at a 2θ value of 3.3° ± 0.2°, and has characteristic peaks at at least four of 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2°, or 24.5 ± 0.2°.

[0009] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form has a characteristic peak at a 2θ value of 3.3° ± 0.2°, and has characteristic peaks at at least five of 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2°, or 24.5 ± 0.2°.

[0010] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form has characteristic peaks at 2θ values of 3.3° ± 0.2°, 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2°, and 24.5 ± 0.2°.

[0011] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form is substantially consistent with Figure 1A , Figure 2A , Figure 3A or Figure 4A is consistent with, for example, Figure 1A is consistent.

[0012] In some embodiments, the differential scanning calorimetry curve of this crystal form has at least one characteristic thermal event in the range of 57°C to 58°C.

[0013] In some embodiments, the differential scanning calorimetry curve of this crystal form has at least one characteristic thermal event in the range of 58°C to 59°C.

[0014] In some embodiments, the differential scanning calorimetry curve of this crystal form is substantially consistent withFigure 1B , Figure 2B , Figure 3B or Figure 4B be consistent, for example, consistent with Figure 1B .

[0015] One or more embodiments of the present specification provide a method for preparing a crystal form as described in the embodiments of the present specification. The method includes method a), method b) or method c).

[0016] Method a) includes the following steps:

[0017] Dissolve acequinocyl of formula I in a crystallization solvent, heat to 55 °C to 70 °C, cool for crystallization, and filter to obtain the crystal form.

[0018] In some embodiments, in method a), the weight ratio of the crystallization solvent to acequinocyl of formula I is (0.5 - 10):1, preferably (1 - 5):1.

[0019] In some embodiments, in method a), the crystallization temperature of acequinocyl of formula I is 0 °C to 70 °C, such as 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C or 65 °C, preferably 5 °C to 20 °C.

[0020] In some embodiments, in method a), the crystallization solvent is one or more of alcohols, ethers, and hydrocarbons. Among them, the alcohols can be one or more of methanol, ethanol, and isopropanol, the ethers can be 2 - methyltetrahydrofuran, and the hydrocarbons can be one or more of n - hexane, cyclohexane, n - pentane, and n - heptane. Preferably, the crystallization solvent is one or more of methanol, ethanol, and 2 - methyltetrahydrofuran.

[0021] Method b) includes the following steps:

[0022] Directly heat acequinocyl of formula I to 55 °C to 70 °C for melting, cool for slicing to obtain the crystal form.

[0023] In some embodiments, in method b), the slicing temperature of acequinocyl of formula I is 0 °C to 70 °C, such as 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C or 65 °C, preferably 5 °C to 20 °C.

[0024] Among them, method c) includes the following steps:

[0025] Directly heat acequinocyl of formula I to 55 °C to 70 °C for melting, cool for crystallization, and filter to obtain the crystal form.

[0026] In some embodiments, in method c), the crystallization temperature of acequinocyl of formula I is from 0°C to 70°C, such as 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C or 65°C, preferably from 5°C to 20°C.

[0027] One or more embodiments of the present specification provide an agrochemical composition. The agrochemical composition includes a crystal form as described in the embodiments of the present specification and one or more excipients or additives.

[0028] One or more embodiments of the present specification provide a method for controlling agricultural pests. The method includes subjecting agricultural pests or the area where they are located to the crystal form as described in the embodiments of the present specification or to an agrochemical composition including the crystal form and one or more excipients or additives. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The present specification will be further described by way of exemplary embodiments, which will be described in detail through the accompanying drawings. These embodiments are not restrictive, and in these embodiments, the same numbers represent the same structures, where:

[0030] Figure 1A is the X-ray powder diffraction pattern of the crystal form of acequinocyl prepared in Example 1 of the present specification;

[0031] Figure 1B is the differential scanning calorimetry curve of the crystal form of acequinocyl prepared in Example 1 of the present specification;

[0032] Figure 2A is the X-ray powder diffraction pattern of the crystal form of acequinocyl prepared in Example 2 of the present specification;

[0033] Figure 2B is the differential scanning calorimetry curve of the crystal form of acequinocyl prepared in Example 2 of the present specification;

[0034] Figure 3A is the X-ray powder diffraction pattern of the crystal form of acequinocyl prepared in Example 3 of the present specification;

[0035] Figure 3B is the differential scanning calorimetry curve of the crystal form of acequinocyl prepared in Example 3 of the present specification;

[0036] Figure 4A is the X-ray powder diffraction pattern of the crystal form of acequinocyl prepared in Example 4 of the present specification;

[0037] Figure 4B is the differential scanning calorimetry curve of the crystal form of acequinocyl prepared in Example 4 of the present specification;

[0038] Figure 5AIt is the X-ray powder diffraction pattern of the crystal form of acequinocyl in Comparative Example 1 of this specification;

[0039] Figure 5B It is the differential scanning calorimetry curve of the crystal form of acequinocyl in Comparative Example 1 of this specification;

[0040] Figure 6 It is the photo of the stability determination after the thermal storage of Comparative Example 1 of this specification is transferred to room temperature for 2 hours;

[0041] Figure 7A It is the photo of the stability determination after the thermal storage of Example 1 of this specification is transferred to room temperature for 2 hours;

[0042] Figure 7B It is the photo of the stability determination after the thermal storage of Example 1 of this specification is transferred to room temperature for 14 days;

[0043] Figure 8A It is the photo of the stability determination after the thermal storage of Example 1 of this specification is transferred to room temperature for 1 month;

[0044] Figure 8B It is the photo of the stability determination after the thermal storage of Example 2 of this specification is transferred to room temperature for 1 month;

[0045] Figure 8C It is the photo of the stability determination after the thermal storage of Example 3 of this specification is transferred to room temperature for 1 month;

[0046] Figure 8D It is the photo of the stability determination after the thermal storage of Example 4 of this specification is transferred to room temperature for 1 month. Detailed implementation mode

[0047] As shown in this specification and the claims, unless the context clearly indicates an exceptional situation, words such as "a", "an", "one" and / or "the" are not specifically singular and may also include the plural. Generally speaking, the terms "comprising" and "including" only indicate the inclusion of the clearly identified steps and elements, and these steps and elements do not constitute an exclusive list, and the method or device may also include other steps or elements.

[0048] The numerical ranges used herein are for concisely expressing each numerical value included in the range.

[0049] Acequinocyl (2-(acetoxy)-3-dodecyl-1,4-naphthoquinone) is a naphthoquinone derivative and belongs to a contact acaricide, which can kill lice, mites and other invertebrates. Because of its lack of systemic activity, it is widely used for the control of mite damage in fruit trees (such as pears, peaches, citrus fruits, etc.), vegetables (such as tomatoes, eggplants, peppers, etc.), etc.

[0050] Acequinocyl is a pale yellow powdery solid at room temperature, with a relatively low melting point, good stability, insoluble in water, and more soluble in organic solvents (such as toluene, dichloromethane, ethyl acetate, etc.).

[0051] Current pesticide formulations include Suspension Concentrate (SC) formulations (also known as suspending agents, aqueous suspension agents, etc.) and Emulsion Concentrate (EC) formulations (also known as suspoemulsion, etc.). As two common formulation dispersion systems, they play an important role in the pesticide field. Under the same efficacy, the SC formulation has lower phytotoxicity than the EC formulation. Therefore, from the perspective of health and environmental protection, pesticide formulations tend to be prepared as the former. However, if the existence form of the solid dispersion phase in the SC formulation is unstable, polymorphic transformation may occur, resulting in an increase in crystal particle size, making the formulation appear thicker and potentially solidify (the solid particles in the suspension gradually aggregate and tend to form a solid under specific conditions), which may further block the application components of agricultural application equipment (equipment used for operations such as fertilization, seeding, irrigation, spraying, etc. in agricultural production, such as pesticide sprayers) during the spraying process of pesticide formulations (specific components for implementing operations, such as the spray nozzles of pesticide sprayers).

[0052] It can be understood that due to the low melting point of acequinocyl, during the processing and heating of the suspending agent, etc., it is more likely to exhibit phenomena such as an increase in particle size and pasting and caking, with weak stability, which easily leads to product deterioration, greatly limiting the application of acequinocyl in suspending agents. In addition, the low starting temperature of the melting range, long melting range, and unstable crystal form of the acequinocyl technical material are also considered important reasons for the easy occurrence of pasting and poor fluidity when preparing the acequinocyl suspending agent.

[0053] Generally, by changing the adjuvant system and adding special adjuvants, the stability of the acequinocyl suspending agent is improved. It should be noted that special adjuvants often cause other problems such as increased production costs and higher production requirements.

[0054] In the examples of this specification, a suspending agent is prepared using a specific crystal form of acequinocyl. This crystal form of acequinocyl has a higher melting point, a higher starting temperature of the melting range, and a shorter melting range, making the prepared acequinocyl suspending agent (i.e., the agrochemical composition described later) have better stability and is not prone to problems such as pasting. Compared with preparing the acequinocyl suspending agent using special adjuvants, it has lower costs and more convenient operation, and can be more widely applied to the control of agricultural pests.

[0055] One of the examples of this specification provides a crystal form of acequinocyl of formula I. The formula I of acequinocyl (i.e., the structural formula) can be The molecular formula corresponding to formula I is C 24 H 32O4, with a relative molecular mass of 384.51 and a CAS number (Chemical Abstracts Service Registry Number) of 57960-19-7.

[0056] During the crystallization process of a substance, due to different intra- or intermolecular bonding modes, the molecules or atoms are arranged differently in the lattice space, resulting in different crystal structures. These different crystal structures are called different crystal forms. For the same substance in different crystal forms, even if the constituent elements are exactly the same, due to their different crystal forms, the physical, chemical, and biological properties exhibited are also different.

[0057] Crystal form detection methods are mainly divided into two categories: physical methods and chemical methods. Physical methods use the differences in the physical properties of substances for crystal form detection. Commonly used physical methods include X-ray Diffraction (XRD) method, thermal analysis method, etc. Chemical methods use the differences in the chemical properties of substances for crystal form detection. Commonly used chemical methods include solubility methods (solubility refers to the concentration of a substance in a solvent when it reaches a saturated state at a certain temperature and pressure. The solubility of different crystal forms is different, and the crystal form of a substance can be determined by measuring the solubility).

[0058] X-ray diffraction method is a method that uses the diffraction phenomenon of X-rays in crystals to study the phase and crystal structure of substances. When X-rays are projected onto a crystal, the atoms in the crystal will scatter the X-rays. Since the atoms are arranged periodically in the crystal, interference will occur between these scattered waves, resulting in reinforcement in certain directions, forming a diffraction phenomenon and obtaining a diffraction pattern. The distribution and intensity of this diffraction pattern are closely related to the crystal structure. Therefore, the phase and crystal structure of a substance can be determined by analyzing the diffraction pattern. The X-ray diffraction method has the advantages of fast detection speed, high precision, wide application range, etc., and is one of the important methods for crystal form detection.

[0059] X-ray diffraction method can include Single Crystal X-ray Diffraction (SXRD) and Powder X-Ray Diffraction (PXRD). The main difference between the two lies in the state and structure of the detection object. The detection object of the former is usually a single crystal sample, and the detection object of the latter is usually a powdered polycrystalline sample.

[0060] In X-ray powder diffraction method, copper (Cu) target is usually used as the anode target material. When a high-energy electron beam bombards the copper target, inner electrons are ionized. When outer electrons jump to the inner vacancies, multiple non-continuous characteristic X-ray spectra are released. Among them, when the K-layer electrons are electrically excited and the waves emitted during the filling of outer electrons are called Cu-Kα rays (i.e., Cu-Kα radiation). Using Cu-Kα rays (i.e., Cu-Kα radiation) for experiments, an X-ray powder diffraction pattern (which can be abbreviated as XRPD pattern) can be obtained, which usually shows multiple diffraction peaks. It can be understood that the abscissa of the X-ray powder diffraction pattern is the angle 2θ, representing the angle between the crystal plane and the X-ray (i.e., Cu-Kα ray) in the crystal. Different crystal structures will produce diffraction peaks at specific angles, and these angles are related to the interplanar spacing of the crystal. Through Bragg's law (i.e., 2dsinθ = nλ, where d is the interplanar spacing, θ is the diffraction angle, and λ is the X-ray wavelength), the interplanar spacing of the crystal can be calculated, thereby inferring the crystal structure type. In addition, by analyzing the intensity, shape, etc. of the diffraction peaks, information such as the unit cell parameters, phase composition, crystal defects, and stress state of the crystal can also be determined.

[0061] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of the crystal form of acequinocyl of Formula I can have characteristic peaks at least at one of 2θ values of 3.3° ± 0.2°, 6.7° ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6° ± 0.2°, 17.1° ± 0.2°, 22.1° ± 0.2°, or 24.5° ± 0.2°. A characteristic peak refers to a diffraction peak with a unique position and intensity in the X-ray powder diffraction pattern, and its intensity and position can identify the crystal structure. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form can have characteristic peaks at 2θ values of 3.3° ± 0.2°, 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2°, and 24.5 ± 0.2°.

[0062] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may also have characteristic peaks at least at two of the 2θ values of 3.3° ± 0.2°, 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2° or 24.5 ± 0.2°. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 3.3° ± 0.2° and 10.4° ± 0.2°. For another example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 3.3° ± 0.2° and 13.5° ± 0.2°.

[0063] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may also have characteristic peaks at least at three of the 2θ values of 3.3° ± 0.2°, 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2° or 24.5 ± 0.2°. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 3.3° ± 0.2°, 13.5° ± 0.2° and 10.4° ± 0.2°. For another example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 3.3° ± 0.2°, 10.4° ± 0.2° and 22.1° ± 0.2°.

[0064] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may also have characteristic peaks at least at four of the 2θ values of 3.3° ± 0.2°, 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2° or 24.5 ± 0.2°. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 3.3° ± 0.2°, 10.4° ± 0.2°, 13.5° ± 0.2° and 22.1° ± 0.2°. For another example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 3.3° ± 0.2°, 10.4° ± 0.2°, 13.5° ± 0.2° and 24.5° ± 0.2°.

[0065] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may also have characteristic peaks at least at five of the 2θ values of 3.3°±0.2°, 6.7±0.2°, 10.4°±0.2°, 11.0°±0.2°, 13.5°±0.2°, 14.6±0.2°, 17.1±0.2°, 22.1°±0.2° or 24.5±0.2°. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 3.3°±0.2°, 10.4°±0.2°, 11.0°±0.2°, 13.5°±0.2° and 22.1°±0.2°. Again, for example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 3.3°±0.2°, 10.4°±0.2°, 11.0°±0.2°, 13.5°±0.2° and 24.5°±0.2°.

[0066] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may also have characteristic peaks at least at six of the 2θ values of 3.3°±0.2°, 6.7±0.2°, 10.4°±0.2°, 11.0°±0.2°, 13.5°±0.2°, 14.6±0.2°, 17.1±0.2°, 22.1°±0.2° or 24.5±0.2°. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 3.3°±0.2°, 10.4°±0.2°, 11.0°±0.2°, 13.5°±0.2°, 22.1°±0.2° and 24.5°±0.2°. Again, for example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at the 2θ values of 10.4°±0.2°, 11.0°±0.2°, 13.5°±0.2°, 22.1°±0.2°, 24.5°±0.2° and 17.1°±0.2°.

[0067] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form has characteristic peaks at the 2θ values of 3.3°±0.2°, 6.7±0.2°, 10.4°±0.2°, 11.0°±0.2°, 13.5°±0.2°, 14.6±0.2°, 17.1±0.2°, 22.1°±0.2° and 24.5±0.2°. It can be understood that, in certain cases, the crystal form of acarifene of formula I described in this specification may include all of the above characteristic peaks.

[0068] By limiting the position of the characteristic peak, the crystal structure-related information of this crystal form can be accurately determined based on the X-ray powder diffraction method. For more content about the X-ray powder diffraction pattern, reference can be made to the relevant descriptions in Examples 1-4 below, which will not be elaborated here.

[0069] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of the crystal form of acequinocyl of Formula I may have a characteristic peak at a 2θ value of 3.3° ± 0.2°. It can be understood that this characteristic peak is the main characteristic peak of the crystal form of acequinocyl of Formula I in this embodiment. Based on the comprehensive evaluation of the angle, d value, and intensity of the peak, by limiting the position of this characteristic peak, this crystal form can be accurately identified, improving the identification efficiency of this crystal form.

[0070] In some embodiments, using Cu-Kα radiation, the X-ray powder diffraction pattern of the crystal form of acequinocyl of Formula I has a characteristic peak at a 2θ value of 3.3° ± 0.2° and at least two characteristic peaks at 2θ values of 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2°, or 24.5 ± 0.2°. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at 2θ values of 3.3° ± 0.2°, 10.4° ± 0.2°, and 11.0° ± 0.2°. Another example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at 2θ values of 3.3° ± 0.2°, 6.7° ± 0.2°, and 11.0° ± 0.2°.

[0071] In some embodiments, the X-ray powder diffraction pattern of this crystal form may also have a characteristic peak at a 2θ value of 3.3° ± 0.2° and at least three characteristic peaks at 2θ values of 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2°, or 24.5 ± 0.2°. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at 2θ values of 3.3° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, and 14.6 ± 0.2°. Another example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at 2θ values of 3.3° ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, and 13.5° ± 0.2°.

[0072] In some embodiments, the X-ray powder diffraction pattern of this crystal form may further have a characteristic peak at a 2θ value of 3.3° ± 0.2° and at least four characteristic peaks at 2θ values of 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2° or 24.5 ± 0.2°. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at 2θ values of 3.3° ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2° and 22.1° ± 0.2°. As another example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at 2θ values of 3.3° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 22.1° ± 0.2° and 24.5 ± 0.2°.

[0073] In some embodiments, the X-ray powder diffraction pattern of this crystal form may further have a characteristic peak at a 2θ value of 3.3° ± 0.2° and at least five characteristic peaks at 2θ values of 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6 ± 0.2°, 17.1 ± 0.2°, 22.1° ± 0.2° or 24.5 ± 0.2°. For example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at 2θ values of 3.3° ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 17.1 ± 0.2° and 22.1° ± 0.2°. As another example, using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystal form may have characteristic peaks at 2θ values of 3.3° ± 0.2°, 6.7 ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2° and 22.1° ± 0.2°.

[0074] By further defining the positions of other characteristic peaks of this crystal form on the basis of defining the main characteristic peaks, the determination process of the crystal form of acequinocyl of Formula I in the embodiments of this specification can be made more accurate.

[0075] Thermal analysis is a method for determining crystal forms by utilizing physical changes (such as melting, evaporation, etc.) or chemical changes (such as thermal decomposition, oxidation, etc.) that occur during the heating or cooling of a substance, and analyzing the measured thermal analysis curves (such as differential scanning calorimetry curves, thermogravimetric curves, etc.). Thermal analysis methods can include differential scanning calorimetry (DSC) method, thermogravimetric analysis (TGA) method, etc.

[0076] Differential scanning calorimetry is a method for measuring the relationship between the thermal power difference between a sample and a reference and temperature. When a thermal reaction (such as endothermic or exothermic) occurs in the sample, the differential scanning calorimetry system records the heat change and generates a differential scanning calorimetry curve (which can be abbreviated as a DSC curve). This curve has the heat flow rate (which refers to the heat absorbed or released by a unit mass of the sample per unit time, with the unit of milliwatt per milligram, i.e., mW / mg) as the vertical coordinate and the temperature T as the horizontal coordinate. By further analyzing this curve, various thermal properties of the sample during the temperature change process can be determined, such as phase transition, melting point, crystallization, chemical reaction, and glass transition, etc.

[0077] In some embodiments, the differential scanning calorimetry curve of the crystal form of acequinocyl of formula I obtained at a heating rate of 5 °C / min may have at least one characteristic thermal event in the range of 55 °C to 60 °C. A characteristic thermal event refers to an endothermic or exothermic phenomenon that occurs and reflects the thermal property change of the substance (the crystal form of acequinocyl of formula I) at a specific temperature. For example, an endothermic event or an exothermic event, where the endothermic event appears as an upward peak on the differential scanning calorimetry curve, indicating that the sample absorbs heat in a certain temperature range and is common in processes such as melting, decomposition, desorption, etc.; the exothermic event appears as a downward peak on the differential scanning calorimetry curve, indicating that the sample releases heat in a certain temperature range and is common in processes such as crystallization, oxidation, solidification, etc.

[0078] In some embodiments, the differential scanning calorimetry curve of the crystal form of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 55.5 °C to 59.5 °C. In some embodiments, the differential scanning calorimetry curve of the crystal form of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 56 °C to 59 °C. In some embodiments, the differential scanning calorimetry curve of the crystal form of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 56.5 °C to 58.5 °C. In some embodiments, the differential scanning calorimetry curve of the crystal form of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 57.0 °C to 58.5 °C.

[0079] In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 56 °C to 58 °C. In some embodiments, in some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 56.5 °C to 58 °C. In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 56.96 °C to 57.55 °C.

[0080] In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 57 °C to 59 °C. In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 57.5 °C to 59 °C. In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I may also have at least one characteristic thermal event in the range of 57.84 °C to 58.51 °C.

[0081] In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I may have at least one characteristic thermal event in the range of 57 °C to 58 °C. In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I may also have at least one characteristic thermal event in the range of 57.2 °C to 57.8 °C. In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I may also have at least one characteristic thermal event in the range of 57.4 °C to 57.6 °C. In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I may also have at least one characteristic thermal event in the range of 57.03 °C to 57.81 °C. The differential scanning calorimetry curve of the polymorph of acequinocyl of formula I obtained at a heating rate of 5 °C / min may also have at least one characteristic thermal event in the range of 57.32 °C to 57.58 °C.

[0082] In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I may have at least one characteristic thermal event in the range of 58 °C to 59 °C. In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I may also have at least one characteristic thermal event in the range of 58.2 °C to 58.8 °C. In some embodiments, the differential scanning calorimetry curve of the polymorph of acequinocyl of formula I may also have at least one characteristic thermal event in the range of 58.4 °C to 58.6 °C.

[0083] In some embodiments, the differential scanning calorimetry curve of the crystalline form of acequinocyl of formula I obtained at a heating rate of 5 °C / min may have at least one characteristic thermal event not only in the range of 55 °C to 60 °C, but also in other temperature ranges. For example, the differential scanning calorimetry curve of the crystalline form of acequinocyl of formula I may have one characteristic thermal event in each of the ranges of 54.14 °C to 54.89 °C and 57.32 °C to 57.58 °C.

[0084] By defining the temperature range of the characteristic thermal event, the thermodynamic relevant information of this crystalline form can be accurately determined based on differential scanning calorimetry, and together with the crystal structure related information obtained by the aforementioned X-ray powder diffraction method, etc., the crystalline form described in the embodiments of this specification can be determined. For more content about the differential scanning calorimetry curve, reference can be made to the relevant descriptions in Examples 1-4 below, which will not be elaborated here.

[0085] In some embodiments of this specification, by providing a crystalline form of acequinocyl of formula I, formula I is Using Cu-Kα radiation, the X-ray powder diffraction pattern of this crystalline form has characteristic peaks at least at one of the 2θ values of 3.35° ± 0.2°, 10.11° ± 0.2°, 10.42° ± 0.2°, 10.96° ± 0.2°, 13.52° ± 0.2°, 20.36° ± 0.2°, or 22.06° ± 0.2°; the differential scanning calorimetry curve of this crystalline form obtained at a heating rate of 5 °C / min has at least one characteristic thermal event in the range of 55 °C to 60 °C, and a new crystalline form of acequinocyl is proposed. Compared with the existing acequinocyl crystals, it has a higher melting point and the starting temperature of the melting range, a shorter melting range. These characteristics make it not easy to appear phenomena such as pasting during the preparation of the aqueous suspension agent. While obtaining a higher quality, better performance and longer storage time of the acequinocyl suspension agent, it also improves the application of the acequinocyl suspension agent product to a certain extent.

[0086] One of the embodiments of this specification provides a method for preparing the crystalline form of acequinocyl of formula I as described in the embodiments of this specification. In some embodiments, this preparation method may include method a), method b), or method c).

[0087] In some embodiments, methods a), b), and c) can all be carried out in a reaction vessel of a certain volume. For example, it can be carried out in a 10 L reaction kettle.

[0088] In some embodiments, method a) may include dissolving acequinocyl of formula I in a crystallization solvent, heating to 55 °C to 70 °C, cooling and crystallizing, and then filtering to obtain this crystalline form.

[0089] Preferably, heat up to 56°C to 69°C. Preferably, heat up to 57°C to 68°C. Preferably, heat up to 58°C to 67°C. Preferably, heat up to 59°C to 66°C. Preferably, heat up to 60°C to 65°C. Preferably, heat up to 61°C to 64°C. Preferably, heat up to 62°C to 63°C. Preferably, heat up to 60°C.

[0090] The crystallization solvent refers to a liquid that can assist the solute to precipitate to form crystals during the crystallization process. In some embodiments, the crystallization solvent can be one or more of alcohols, ethers, and hydrocarbons. In some embodiments, the aforementioned alcohols can be one or more of methanol, ethanol, and isopropanol. In some embodiments, the aforementioned ether can be 2-methyltetrahydrofuran. In some embodiments, the aforementioned hydrocarbons can be one or more of n-hexane, cyclohexane, n-pentane, and n-heptane. In some embodiments, preferably, the crystallization solvent can be one or more of methanol, ethanol, and 2-methyltetrahydrofuran. It can be understood that selecting a suitable crystallization solvent is a key factor in ensuring crystal quality and improving crystallization efficiency. By defining the preferred crystallization solvent, the crystallization process of the acequinocyl crystal form described in the embodiments of this specification can be ensured to proceed smoothly, and high-quality crystals can be obtained as much as possible.

[0091] In some embodiments, in method a), the weight ratio of the crystallization solvent to acequinocyl of formula I can be (0.5 - 10):1. It can be understood that if the weight ratio of the crystallization solvent to acequinocyl of formula I is too high (i.e., too much crystallization solvent), a hot saturated solution may not be formed, so that acequinocyl cannot precipitate or cannot precipitate in the form of crystals during cooling, the amount of crystallization decreases, and the yield decreases; if the weight ratio of the crystallization solvent to acequinocyl of formula I is too low (i.e., too little crystallization solvent), part of the acequinocyl may not be completely dissolved during heating, resulting in residues in the finished product and affecting crystal quality. By setting the weight ratio of the crystallization solvent to acequinocyl of formula I to be (0.5 - 10):1, an appropriate ratio of solute to solvent can be ensured, facilitating subsequent crystallization. Preferably, in method a), the weight ratio of the crystallization solvent to acequinocyl of formula I can also be (0.7 - 8):1. Preferably, in method a), the weight ratio of the crystallization solvent to acequinocyl of formula I can also be (0.9 - 6):1. Preferably, in method a), the weight ratio of the crystallization solvent to acequinocyl of formula I can also be (1 - 5):1. Preferably, in method a), the weight ratio of the crystallization solvent to acequinocyl of formula I can also be (2 - 4):1. Preferably, in method a), the weight ratio of the crystallization solvent to acequinocyl of formula I can also be 3:1. By setting the preferred weight ratio, a solute solution ratio with as excellent crystal quality and as high yield as possible for the finished product crystals can be determined.

[0092] The crystallization temperature refers to the temperature during crystallization (i.e., the temperature after the aforementioned cooling). In some embodiments, the crystallization temperature of acequinocyl of Formula I can be 0°C to 70°C. It can be understood that the change in temperature will directly affect the crystallization process and results. Too high or too low crystallization temperature may lead to crystallization failure. If the crystallization temperature is too high, the substance may melt and lose its crystal structure, and stable crystals cannot be formed. If the crystallization temperature is too low, the molecular motion of the substance will slow down, and the crystallization rate will become slower or even stop. By setting the crystallization temperature of acequinocyl of Formula I to 0°C to 70°C, normal precipitation of crystals can be ensured, and adverse consequences such as crystal defects and low crystallization rate caused by inappropriate crystallization temperature can be avoided. Preferably, the crystallization temperature of acequinocyl of Formula I can also be 1°C to 60°C. Preferably, the crystallization temperature of acequinocyl of Formula I can also be 2°C to 50°C. Preferably, the crystallization temperature of acequinocyl of Formula I can also be 3°C to 40°C. Preferably, the crystallization temperature of acequinocyl of Formula I can also be 4°C to 30°C. Preferably, the crystallization temperature of acequinocyl of Formula I can also be 5°C to 20°C. Preferably, the crystallization temperature of acequinocyl of Formula I can also be 6°C to 10°C. Preferably, the crystallization temperature of acequinocyl of Formula I can also be 5°C to 10°C. Preferably, the crystallization temperature of acequinocyl of Formula I can also be 7°C to 9°C. Preferably, the crystallization temperature of acequinocyl of Formula I can also be 8°C to 9°C. By setting the preferred crystallization temperature, the precipitation rate of crystals can be appropriate, and the quality of the crystals can be as good as possible.

[0093] For more content about method a), reference can be made to the relevant descriptions in Examples 1, 2, and 4 described below.

[0094] In some embodiments, method b) can include directly heating acequinocyl of Formula I to 55°C to 70°C for melting, and then cooling and slicing to obtain this crystal form.

[0095] Preferably, heat to 56°C to 69°C. Preferably, heat to 57°C to 68°C. Preferably, heat to 58°C to 67°C. Preferably, heat to 59°C to 66°C. Preferably, heat to 60°C to 65°C. Preferably, heat to 61°C to 64°C. Preferably, heat to 52°C to 63°C. Preferably, heat to 60°C to 70°C. Preferably, heat to 61°C to 69°C. Preferably, heat to 62°C to 68°C. Preferably, heat to 53°C to 67°C. Preferably, heat to 54°C to 65°C.

[0096] For more content about method b), reference can be made to the relevant description in Example 3 described below.

[0097] In some embodiments, method c) can include directly heating acequinocyl of Formula I to 55°C to 70°C for melting, cooling and crystallizing, and then filtering to obtain this crystal form.

[0098] Preferably, heat up to 56°C to 69°C. Preferably, heat up to 57°C to 68°C. Preferably, heat up to 58°C to 67°C. Preferably, heat up to 59°C to 66°C. Preferably, heat up to 60°C to 65°C. Preferably, heat up to 61°C to 64°C. Preferably, heat up to 62°C to 63°C. Preferably, heat up to 60°C.

[0099] In some embodiments, the crystallization temperature for cooling crystallization can be the same as the crystallization temperature in method a).

[0100] In some embodiments of the present specification, by using method a), method b) or method c) to prepare the crystal form of acequinocyl of formula I, it can be ensured that the desired crystal form of acequinocyl can be obtained.

[0101] In some embodiments, when the reaction solvent for the acequinocyl synthesis reaction is the same as the crystallization solvent described in the embodiments of the present specification, a part of the reaction solvent of the reaction solution containing acequinocyl can be evaporated or without any treatment, dissolved in the crystallization solvent, first heated up to 55°C to 70°C, and then cooled down to 0°C to 60°C, crystallized and filtered, and the desired crystal form of acequinocyl can also be obtained. Technical solutions that are the same as or similar to this solution also belong to the inventive concept of the embodiments of the present specification.

[0102] One or more embodiments of the present specification provide an agrochemical composition. The agrochemical composition includes the crystal form as described in the embodiments of the present specification and one or more excipients or additives.

[0103] An agrochemical composition refers to a mixture of various chemical substances that can be used in agricultural production. For example, chemical fertilizers, pesticides, etc. The agrochemical composition can be in various forms. For example, the agrochemical composition can be in the form of a soluble liquid concentrate, an emulsion concentrate, a microemulsion, a suspension concentrate, a water-dispersible powder or granules, etc. In some embodiments, preferably, the agrochemical composition can be in the form of a suspension concentrate. For example, the agrochemical composition can be in the form of a suspending agent (i.e., the aforementioned suspension concentrate). In some embodiments, the agrochemical composition can be an acequinocyl suspending agent.

[0104] In some embodiments, the acaracide composition contains the acaracide of the aforementioned crystalline form in an amount of about 1% to about 99% by weight of the composition. In some embodiments, the acaracide composition contains the acaracide of the aforementioned crystalline form in an amount of about 10% to about 90% by weight of the composition. In some embodiments, the acaracide composition contains the acaracide of the aforementioned crystalline form in an amount of about 20% to about 80% by weight of the composition. In some embodiments, the acaracide composition contains the acaracide of the aforementioned crystalline form in an amount of about 30% to about 70% by weight of the composition. In some embodiments, the acaracide composition contains the acaracide of the aforementioned crystalline form in an amount of about 40% to about 60% by weight of the composition. In some embodiments, the acaracide composition contains the acaracide of the aforementioned crystalline form in an amount of about 50% by weight of the composition. It can be understood that the amount of acaracide used in the composition can be adjusted according to the desired acaricidal effect, formulation stability effect, etc.

[0105] An excipient refers to a substance that aids in the formation of a formulation. An additive refers to an auxiliary substance added during the processing or use of a formulation. In some embodiments, the excipient or additive can be selected from adjuvants or surfactants, including but not limited to wetting agents, emulsifiers, dispersants, viscosity regulators, defoamers, antifreeze agents, pH regulators, stabilizers, anti-caking agents, etc.

[0106] In some embodiments, in addition to the acaracide of the aforementioned crystalline form, the acaracide composition may further contain other active ingredients. In some embodiments, the aforementioned other active ingredients may be one or more other insecticides, acaricides, etc. For example, organophosphorus, carbamates, pyrethroids, etc. In some embodiments, the aforementioned other active ingredients may be one or more herbicides or fungicides. For example, diphenyl ethers, triazolone, organic amines, etc.

[0107] One or more embodiments of the present specification provide a method for controlling agricultural pests. The method includes subjecting agricultural pests or their habitats to the crystalline form as described in the embodiments of the present specification or to the agrochemical composition as described in the embodiments of the present specification.

[0108] The crystalline form of the acaracide of formula I and its preparation method described in the embodiments of the present specification will be elaborated in detail below through Examples 1 - 4 and Comparative Example 1. It should be noted that the reaction conditions, reaction materials, and amounts of reaction materials in Examples 1 - 4 and Comparative Example 1 are only for illustrating the crystalline form of the acaracide of formula I and its preparation method, and do not limit the protection scope of the present application. Detection Method

[0109] Differential Scanning Calorimetry:

[0110] Analytical Instrument: NETZSCH DCS214;

[0111] Measurement method and parameters: Heating rate is 5 °C / min; rising from 0 °C to 150 °C.

[0112] X-ray powder diffraction:

[0113] Instrument model: PANalytical Empyrean;

[0114] Testing method and parameters: Obtain the spectrum using a copper radiation target at a scanning speed of 0.02° per minute. Example 1

[0115] Put 2.24 kg of crude acequinocyl of formula I (purity 95%) into a 10 L reactor, then add 4 kg of methanol (i.e., the aforementioned crystallization solvent), heat up to 60 °C, and after all the acequinocyl of formula I is dissolved, slowly cool down to 5 °C - 10 °C (i.e., the aforementioned crystallization temperature), filter to obtain 2.11 kg of Product 1. The purity of Product 1 is 99% and the yield is 94%.

[0116] Figure 1A is the X-ray powder diffraction pattern of Example 1. As Figure 1A shown, Product 1 has characteristic peaks at 2θ values of 3.3465°, 6.7245°, 10.4289°, 10.9607°, 13.5235°, 14.5662°, 17.1189°, 22.0684°, 26.6359°.

[0117] Figure 1B is the differential scanning calorimetry curve of Example 1. As Figure 1B shown, Product 1 has a characteristic thermal event in the range of 57.03 °C - 57.81 °C.

[0118] From Figure 1A and Figure 1B it can be known that Product 1 prepared by the aforementioned method a) is the crystal form of acequinocyl of formula I described in the aforementioned example.

[0119] The specific data (including diffraction angle, d value, relative intensity of the peak) of the X-ray powder diffraction pattern of Example 1 are shown in Table 1: Table 1 Example 2

[0120] Into a 10 L reactor, 2.24 kg of crude acequinocyl of Formula I (purity: 95%) was charged, and then 4 kg of ethanol (i.e., the aforementioned crystallization solvent) was added. The temperature was raised to 60 °C. After all of the acequinocyl of Formula I was dissolved, the temperature was slowly lowered to 5 °C to 10 °C (i.e., the aforementioned crystallization temperature), and filtration was performed to obtain 2.11 kg of Product 2. The purity of Product 2 was 99%, and the yield was 94%.

[0121] Figure 2A is the X-ray powder diffraction pattern of Example 2. As Figure 2A shown, Product 2 has characteristic peaks at 2θ values of 3.3513°, 6.7269°, 10.4262°, 10.9626°, 13.5256°, 14.5699°, 17.1275°, 22.0641°, and 24.5299°.

[0122] Figure 2B is the differential scanning calorimetry curve of Example 2. As Figure 2B shown, Product 2 has a characteristic thermal event in the range of 56.96 °C to 57.55 °C.

[0123] From Figure 2A and Figure 2B it can be seen that Product 2 prepared by the aforementioned method a) is the crystal form of acequinocyl of Formula I described in the aforementioned example.

[0124] The specific data (including diffraction angle, d value, and relative intensity of the peak) of the X-ray powder diffraction pattern of Example 2 are shown in Table 2: Table 2 Example 3

[0125] Into a 10 L reactor, 2.24 kg of crude acequinocyl of Formula I (purity: 99%) was charged, and the temperature was raised to 60 °C to 70 °C. After all of the acequinocyl of Formula I was melted, it was poured out of the reactor, cooled, and sliced to obtain 2.24 kg of Product 3. The purity of Product 2 was 99%, and the yield was 100%.

[0126] Figure 3A is the X-ray powder diffraction pattern of Example 3. As Figure 3A shown, Product 3 has characteristic peaks at 2θ values of 3.3874°, 6.7684°, 10.4614°, 10.9971°, 13.5633°, 14.6231°, 17.1483°, 22.0848°, and 24.5728°.

[0127] Figure 3B is the differential scanning calorimetry curve of Example 3. As Figure 3BAs shown, Product No. 3 has a characteristic thermal event in the range of 57.84°C to 58.51°C.

[0128] It can be seen from Figure 3A and Figure 3B that Product No. 3 prepared by the aforementioned method b) is the crystal form of acequinocyl of Formula I described in the aforementioned examples.

[0129] The specific data of the X-ray powder diffraction pattern of Example 3 (including diffraction angle, d value, relative intensity of the peaks) are shown in Table 3 as follows: Table 3 Example 4

[0130] 2.24 kg of the crude product of acequinocyl of Formula I (purity 95%) was charged into a 10 L reaction kettle, and then 24 kg of 2-methyltetrahydrofuran (i.e., the aforementioned crystallization solvent) was added. The temperature was raised to 60°C. After all of the acequinocyl of Formula I was dissolved, the temperature was slowly lowered to 15°C to 20°C (i.e., the aforementioned crystallization temperature), and filtration was carried out to obtain 2.11 kg of Product No. 4. The purity of Product No. 4 was 99% and the yield was 94%.

[0131] Figure 4A is the X-ray powder diffraction pattern of Example 4. As Figure 4A shown, Product No. 4 has characteristic peaks at 2θ values of 3.3794°, 6.7564°, 10.4483°, 10.9867°, 13.5568°, 14.5973°, 17.1544°, 22.0885°, and 24.5680°.

[0132] Figure 4B is the differential scanning calorimetry curve of Example 4. As Figure 4B shown, Product No. 4 has a characteristic thermal event in each of the ranges of 54.14°C to 54.89°C and 57.32°C to 57.58°C.

[0133] It can be seen from Figure 4A and Figure 4B that Product No. 4 prepared by the aforementioned method a) is the crystal form of acequinocyl of Formula I described in the aforementioned examples.

[0134] The specific data of the X-ray powder diffraction pattern of Example 4 (including diffraction angle, d value, relative intensity of the peaks) are shown in Table 4 as follows: Table 4 Comparative Example 1

[0135] Comparative Example 1 is a commercially available acequinocyl powder with a purity of 96%.

[0136] Figure 5A is the X-ray powder diffraction pattern of Comparative Example 1. As Figure 5A shown, the characteristic peaks of the commercially available product are mainly distributed at 2θ values of 6.7123, 10.0932, 10.4008, 10.9359, 13.4920, 17.1026, 20.3673, 22.0386, etc.

[0137] Figure 5B is the differential scanning calorimetry curve of Comparative Example 1. As Figure 5B shown, the commercially available product has a characteristic thermal event in the ranges of 42.06 °C to 52.85 °C and 53.06 °C to 55.01 °C respectively.

[0138] From Figure 5A and Figure 5B it can be seen that the commercially available product has a different crystal form from the acequinocyl of Formula I described in the foregoing examples.

[0139] The specific data (including diffraction angle, d value, relative intensity of the peak) of the X-ray powder diffraction pattern of Comparative Example 1 are shown in Table 5: Table 5 Determination of formulation stability and result analysis

[0140] Preparation of aqueous suspension

[0141] The acequinocyl of Formula I in the crystal form described in the examples of this specification (i.e., Products 1-4 in Examples 1-4) and the commercially available acequinocyl (i.e., the commercially available product in Comparative Example 1) were respectively prepared into acequinocyl aqueous suspensions. The specific method is as follows: Mix 10% by weight of acequinocyl, 6.0% by weight of comb-shaped grafted acrylic acid copolymer Atlox 4917 (CRODA), 0.3% by weight of xanthan gum, 0.5% by weight of magnesium aluminum silicate, 0.5% by weight of isothiazolinone, 5% by weight of ethylene glycol, 0.5% by weight of dimethyl silicone oil and water (the balance), shear and mix for a certain time, and then grind the slurry to a particle size less than 5 microns to obtain an aqueous suspension with uniform appearance and dispersible in water.

[0142] Hot storage stability test

[0143] The prepared aqueous suspension was subjected to a 14-day stability determination test at 54 °C (based on GB / T 19136-2021 "Determination Method for Thermal Storage Stability of Pesticides"):

[0144] 1. Figure 6This is a photo of the stability measurement of Comparative Example 1 in this specification after 2 hours of heat storage and returning to room temperature. As Figure 6 shown, it can be seen that the aqueous suspension prepared using commercially available acequinocyl (i.e., the commercially available product in Comparative Example 1) shows obvious pasting phenomenon and poor fluidity after 2 hours of heat storage and returning to room temperature, and cannot meet the requirements of production, transportation and storage.

[0145] 2. Figure 7A This is a photo of the stability measurement of Example 1 in this specification after 2 hours of heat storage and returning to room temperature. As Figure 7A shown, it can be seen that the aqueous suspensions prepared using the crystalline form of acequinocyl of formula I described in the examples of this specification (i.e., Products 1-4 in Examples 1-4) have normal appearance and no pasting phenomenon after 2 hours of heat storage and returning to room temperature, with good fluidity, and can meet the requirements of production, transportation and storage.

[0146] In order to further observe whether the aqueous suspension prepared from the crystalline form of the present invention can adapt to extremely harsh environmental conditions, the time of returning to room temperature after placing at 54 °C for 14 days was extended to 14 days and 1 month respectively: Figure 7B This is a photo of the stability measurement of Example 1 in this specification after 14 days of heat storage and returning to room temperature. As Figure 7B shown, after 14 days, the appearance and fluidity of Example 1 are normal and there is no obvious pasting; Figures 8A - 8D These are photos of the stability measurement of Examples 1-4 in this specification after 1 month of heat storage and returning to room temperature. As Figures 8A - 8D shown, after 1 month, there is no pasting or only a small amount of crystal precipitation in Examples 2, 3, and 4, and the fluidity is good. It can be seen that Examples 1-4 all have good heat storage stability, among which Example 1 is particularly outstanding with the best stability, followed by Examples 2 and 3, and Example 4 is the last.

[0147] Result analysis

[0148] In summary, the crystalline form of acequinocyl of formula I described in the examples of this specification is more suitable for the suspension agent system than the existing acequinocyl. The agrochemical composition (i.e., acequinocyl aqueous suspension) prepared from this crystalline form of acequinocyl shows excellent stability, better fluidity and uniformity at both room temperature and higher temperatures, and is not prone to problems such as pasting. In addition, among the various examples of this crystalline form prepared, in the long term, Example 1 shows better performance, that is, when methanol is used as the crystallization solution, the obtained acequinocyl aqueous suspension formulation is more stable.

[0149] The basic concepts have been described above. Obviously, for those skilled in the art, the above detailed disclosure is only an example and does not constitute a limitation of this specification. Although not explicitly stated here, those skilled in the art may make various modifications, improvements, and corrections to this specification. Such modifications, improvements, and corrections are suggested in this specification, so such modifications, improvements, and corrections still fall within the spirit and scope of the exemplary embodiments of this specification.

[0150] At the same time, this specification uses specific terms to describe the embodiments of this specification. For example, "one embodiment", "an embodiment", and / or "some embodiments" mean a certain feature, structure, or characteristic related to at least one embodiment of this specification. Therefore, it should be emphasized and noted that the "one embodiment" or "an embodiment" or "an alternative embodiment" mentioned twice or more at different positions in this specification does not necessarily refer to the same embodiment. In addition, certain features, structures, or characteristics in one or more embodiments of this specification can be appropriately combined.

[0151] Similarly, it should be noted that, in order to simplify the expression of the disclosure of this specification and thus help the understanding of one or more embodiments of the invention, in the previous description of the embodiments of this specification, sometimes multiple features are grouped into one embodiment, drawing, or description thereof. However, this disclosure method does not mean that the features required by the object of this specification are more than those mentioned in the claims. In fact, the features of the embodiments are less than all the features of the individual embodiments disclosed above.

[0152] In some embodiments, numbers describing the components and attribute quantities are used. It should be understood that such numbers used for the description of embodiments are, in some examples, modified by the modifiers "about", "approximate", or "substantially". Unless otherwise stated, "about", "approximate", or "substantially" indicate that the said numbers allow a variation of ±20%. Accordingly, in some embodiments, the numerical parameters used in the specification and claims are approximate values, and such approximate values can change according to the characteristics required by individual embodiments. In some embodiments, the numerical parameters should consider the specified significant digits and adopt the method of retaining the general number of digits. Although the numerical ranges and parameters used in some embodiments of this specification to confirm the breadth of their ranges are approximate values, in specific embodiments, such numerical settings are as precise as possible within the feasible range.

[0153] For each patent, patent application, patent application publication, and other materials cited in this specification, such as articles, books, specifications, publications, documents, etc., the entire content thereof is hereby incorporated by reference into this specification. Except for the application history documents that are inconsistent with or conflict with the content of this specification, and also except for the documents that limit the broadest scope of the claims of this specification (currently or subsequently appended to this specification). It should be noted that if there are any inconsistencies or conflicts between the descriptions, definitions, and / or uses of terms in the supplementary materials of this specification and the content described in this specification, the descriptions, definitions, and / or uses of terms in this specification shall prevail.

[0154] Finally, it should be understood that the embodiments described in this specification are only used to illustrate the principles of the embodiments of this specification. Other variations may also fall within the scope of this specification. Therefore, by way of example and not limitation, alternative configurations of the embodiments of this specification may be regarded as consistent with the teachings of this specification. Accordingly, the embodiments of this specification are not limited to the embodiments explicitly introduced and described in this specification.

Claims

1. A crystal form of acequinocyl of formula I, characterized in that i) using Cu-Kα radiation, the X-ray powder diffraction pattern of the crystal form has characteristic peaks at least at one of the 2θ values of 3.3° ± 0.2°, 6.7° ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6° ± 0.2°, 17.1° ± 0.2°, 22.1° ± 0.2° or 24.5° ± 0.2°; ii) the differential scanning calorimetry curve of the crystal form obtained with a heating rate of 5 °C / min has at least one characteristic thermal event in the range of 55 °C to 60 °C.

2. The crystalline form according to claim 1, wherein Using the Cu-Kα radiation, the X-ray powder diffraction pattern of the crystal form has a characteristic peak at a 2θ value of 3.3° ± 0.2°.

3. The crystalline form according to claim 2, wherein Using the Cu-Kα radiation, the X-ray powder diffraction pattern of the crystal form has characteristic peaks at least at two of the 2θ values of 6.7° ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6° ± 0.2°, 17.1° ± 0.2°, 22.1° ± 0.2° or 24.5° ± 0.2°.

4. The crystalline form according to claim 3, wherein, Using the Cu-Kα radiation, the X-ray powder diffraction pattern of the crystal form has characteristic peaks at the 2θ values of 6.7° ± 0.2°, 10.4° ± 0.2°, 11.0° ± 0.2°, 13.5° ± 0.2°, 14.6° ± 0.2°, 17.1° ± 0.2°, 22.1° ± 0.2° and 24.5° ± 0.2°.

5. The crystalline form according to claim 1, characterized in that, The differential scanning calorimetry curve of the crystal form has at least one characteristic thermal event in the range of 57 °C to 58 °C.

6. The crystalline form according to claim 1, characterized in that, The differential scanning calorimetry curve of the crystal form has at least one characteristic thermal event in the range of 58 °C to 59 °C.

7. A method for preparing the crystal form according to any one of claims 1-6, characterized in that, Comprising: Method a): Dissolve the acequinocyl of formula I in a crystallization solvent, heat to 55 °C to 70 °C, cool for crystallization, and filter to obtain the crystal form; Method b): Directly heat the acequinocyl of formula I to 55 °C to 70 °C for melting, cool and slice to obtain the crystal form; or Method c): Directly heat the acequinocyl of formula I to 55 °C to 70 °C for melting, cool for crystallization, and filter to obtain the crystal form.

8. The method according to claim 7, characterized in that in the method a), the weight ratio of the crystallization solvent to the acequinocyl of formula I is (0.5 - 10):1, preferably (1 - 5):1; and / or in the methods a) and c), the crystallization temperature of the acequinocyl of formula I is 0 °C to 70 °C, preferably 5 °C to 20 °C; and / or in the method a), the crystallization solvent is one or more of alcohols, ethers, and hydrocarbons; preferably, the alcohols are one or more of methanol, ethanol, and isopropanol, the ether is 2-methyltetrahydrofuran, and the hydrocarbons are one or more of n-hexane, cyclohexane, n-pentane, and n-heptane; more preferably, the crystallization solvent is one or more of methanol, ethanol, and 2-methyltetrahydrofuran.

9. An agrochemical composition comprising a crystalline form as claimed in any one of claims 1 - 6 and one or more excipients or additives.

10. A method for controlling agricultural pests, comprising subjecting the agricultural pests or their locus to a crystalline form as claimed in any one of claims 1 - 6 or to an agrochemical composition comprising the crystalline form and one or more excipients or additives.

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