Salt compound of mesotrione, novel crystal form of mesotrione and preparation method and application of salt compound and novel crystal form of mesotrione

Abstract

The invention discloses a salt compound of mesotrione, a novel crystal form of mesotrione, and a preparation method and application of the mesotrione. The preparation method of the novel mesotrione crystal form comprises the following steps: (1) mixing mesotrione, an alkaline substance and a solvent to obtain a material to be crystallized; (2) crystallizing the material to be crystallized to obtain a new crystal form of mesotrione; during crystallization treatment, the pH value of a crystallization system is greater than or equal to 4. Starting from the mesotrione compound, a series of mesotrione dominant crystal forms with higher chemical stability are screened and developed through the preparation method, meanwhile, the biological activity is improved, and the mesotrione crystal form has a great application prospect.

Description

Technical Field

[0001] This invention relates to the technical field of novel crystal forms of nicosulfuron, and more specifically, to salt compounds of nicosulfuron, novel crystal forms, their preparation methods and applications. Background Technology

[0002] Mesotrione, also known as methyl sulfadiazine, has the chemical name 2-(4-methanesulfonyl-2-nitrobenzoyl)cyclohexane-1,3-dione and the molecular formula C60. 14 H 13 NO7S is a triketone herbicide that targets p-hydroxyphenylpyruvate dioxidase (HPPD). It possesses broad-spectrum herbicidal activity and a wide range of applications, suitable for both pre- and post-emergence application, causing weeds to bleach and die. Its chemical structure is as follows:

[0003]

[0004] Currently, three crystalline forms of mesotrione have been reported: crystalline form 1, crystalline form 2, and crystalline form 3. Crystalline form 1 is the stable crystalline form. Crystalline forms 2 and 3 are thermodynamically unstable and will gradually transform into crystalline form 1. Furthermore, crystalline form 2 readily forms fine microcrystals during preparation, making collection difficult. Therefore, crystalline form 1 is often used as the target crystalline form in industrial production. For example, Chinese patent CN114031527A discloses a large-scale production of crystalline form 1 using a multi-stage continuous crystallization method. However, crystalline form 1 suffers from low chemical stability. Patent WO2012 / 123314 found that crystalline form 1 of mesotrione has low chemical stability; Delphine Lavieille et al. (Understanding mesotrione photochemistry when applied on leaves. Environ. Chem. 2008, 5, 420-425) found that the half-life of crystalline form 1 of mesotrione under light irradiation is only 7 hours. Furthermore, the low stability of nicosulfuron leads to a tendency for its formulations to darken in color during storage, affecting the product's appearance and quality. Therefore, improving the chemical stability of nicosulfuron is one of the key technical challenges hindering its development and application.

[0005] Currently, using adjuvants or compounding agents to form solid compositions of nicosulfuron is a common method to improve the chemical stability of nicosulfuron. Patent CN110022681A discloses a method for preparing and using a solid herbicidal composition containing nicosulfuron and a series of alkaline substances, indicating that this combination can significantly reduce the decomposition of nicosulfuron. Patent CN109874790A discloses a nicosulfuron microcapsule suspension and its preparation method, which improves the stability of nicosulfuron and extends the duration of action of the active ingredient by adding acetochlor and various adjuvants. However, the above methods require the introduction of multiple adjuvants, which may lead to higher production costs and potential environmental risks.

[0006] Crystal engineering can improve the physicochemical properties of drugs by controlling the arrangement and interactions of drug molecules in crystal structures, providing a new approach to enhancing the chemical stability of nicosulfuron. However, the three reported crystal forms of nicosulfuron all exhibit poor stability. Therefore, a more comprehensive and detailed investigation of potential new crystal forms of nicosulfuron is urgently needed to screen for new crystal forms with higher chemical stability. Summary of the Invention

[0007] To address the problems in existing technologies, this invention proposes salt compounds of nicosulfuron, novel crystal forms, their preparation methods, and applications. Starting with nicosulfuron itself, this invention screens and develops a series of nicosulfuron salt compounds and their novel crystal forms with enhanced chemical stability. These compounds improve photothermal stability while also increasing biological activity, demonstrating significant application potential.

[0008] The first aspect of the present invention is to provide a salt compound of nicosulfuron, characterized in that the general structural formula of the salt compound of nicosulfuron is as follows:

[0009]

[0010] Where n is 0 to 3, for example, n is 1, 2, 3; m is 0 to 3, for example, m is 0, 0.5, 1, 1.5, 2, 2.5, 3;

[0011] M n+ It can be a monovalent metal ion, a divalent metal ion, a trivalent metal ion, or an ammonium ion;

[0012] Preferably, the monovalent metal ion is a lithium ion, a sodium ion, or a potassium ion; and / or,

[0013] The divalent metal ion is a magnesium ion, calcium ion, copper ion, zinc ion, manganese ion, ferrous ion, or nickel ion; and / or,

[0014] The trivalent metal ion is an iron ion.

[0015] A second aspect of the present invention is to provide a method for preparing a new crystal form of nicosulfuron, comprising the following steps:

[0016] (1) Mix nicotinamide, alkaline substances and solvents to obtain the material to be crystallized;

[0017] (2) Crystallize the material to be crystallized to obtain a new crystal form of nicosulfuron;

[0018] During the crystallization process, the pH value of the crystallization system is ≥4, for example, the pH value can be 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0019] In existing technologies, the preparation of nicosulfuron crystals typically involves alkali dissolution and acid precipitation (i.e., mixing an alkaline substance with nicosulfuron to form a crystallizable material, then adding an acidic substance during crystallization). This invention, however, achieves alkali dissolution and alkali precipitation (i.e., mixing an alkaline substance with nicosulfuron to form a crystallizable material, then adding an alkaline substance during crystallization). Through this preparation method, a new nicosulfuron crystal with superior performance is obtained.

[0020] Furthermore, current experiments show that the new crystal form of this invention can be obtained in solution as long as the pH value in the crystallization system is ≥4. When pH <4, the crystal form precipitated is that of the prior art (such as crystal form 1, crystal form 2 and crystal form 3 mentioned in the background art).

[0021] The new crystal form of nicosulfuron in this invention refers to the new crystal form obtained by crystallizing the metal salt or ammonium salt of nicosulfuron.

[0022] As a preferred embodiment, step (1),

[0023] The alkaline substance is selected from at least one of the following: salts of metal elements (preferably salts of Group 1 metal elements), oxides of metal elements (preferably oxides of Group 1 metal elements), hydroxides of metal elements (preferably hydroxides of Group 1 metal elements), ammonia, ammonia water, or ammonium salts; preferably, the alkaline substance is selected from at least one of the following: sodium salt, sodium hydroxide, potassium salt, potassium hydroxide, lithium salt, lithium hydroxide, ammonia, ammonia water, or ammonium salts; and / or,

[0024] The solvent is selected from at least one of ketones, alcohols, nitriles, amides, esters, haloalkanes, dimethyl sulfoxide, or water; preferably, the solvent is selected from at least one of ketones, alcohols, nitriles, amides, dimethyl sulfoxide, or water.

[0025] Preferably,

[0026] The sodium salt is selected from at least one of sodium acetate, sodium phosphate, sodium monohydrogen phosphate, sodium carbonate, or sodium bicarbonate; and / or,

[0027] The potassium salt is selected from at least one of potassium acetate, potassium phosphate, potassium monohydrogen phosphate, potassium carbonate, or potassium bicarbonate; and / or,

[0028] The lithium salt is selected from at least one of lithium acetate, lithium phosphate, lithium monohydrogen phosphate, lithium carbonate, or lithium bicarbonate; and / or,

[0029] The ammonium salt is selected from at least one of ammonium acetate, ammonium phosphate, ammonium monohydrogen phosphate, ammonium carbonate, or ammonium bicarbonate; and / or,

[0030] More preferably,

[0031] Ketones are selected from at least one of methyl ethyl ketone or acetone; and / or,

[0032] The alcohols are selected from at least one of methanol, ethanol, propanol, or isopropanol; and / or,

[0033] Nitriles are selected from at least one of acetonitrile or butyronitrile; and / or,

[0034] The amides are selected from at least one of N,N-dimethylformamide or N-methylpyrrolidone.

[0035] As a preferred embodiment, step (1),

[0036] The volume concentration of nicosulfuron is 0.02 g / mL to 0.9 g / mL; preferably 0.25 g / mL to 0.9 g / mL (solid grinding) or 0.02 g / mL to 0.2 g / mL (solution method);

[0037] The molar ratio of nicosulfuron to metal ions or ammonium ions in the alkaline substance is 1:0.3 to 20; preferably 1:0.3 to 1.1 (solid grinding) or 1:2 to 20 (solution method);

[0038] Preferably, the alkaline substance is added in the form of an alkaline substance solution, the concentration of which is 5 wt% to 50 wt%.

[0039] In a preferred embodiment, step (2), the crystallization process is selected from at least one of the following methods:

[0040] Method a) Mix the material to be crystallized with a solution containing the crystallizing material to precipitate a new crystal form of nicosulfuron; preferably, the crystallizing material is selected from at least one salt or hydroxide of a metal element or ammonium ion (preferably selected from at least one salt or hydroxide of lithium, sodium, potassium, or ammonium); more preferably, the concentration of the solution containing the crystallizing material is more than 25% of the saturated solution concentration of the crystallizing material.

[0041] In the technical solution of this invention, the crystallizing material refers to the crystallizing material in a solution containing the crystallizing material;

[0042] Method b) Evaporate the solvent in the material to be crystallized to precipitate a new crystal form of mesotrione;

[0043] Method c) Grind the material to be crystallized to precipitate a new crystal form of mesotrione.

[0044] As a preferred embodiment, in method a),

[0045] In method a), the crystallizing material is selected from at least one of the following: halides, sulfates, nitrates, carbonates, phosphates, acetates, or hydroxides of metal ions or ammonium ions; preferably, the solution containing the crystallizing material is selected from at least one of the following: saturated halide solutions, saturated sulfate solutions, saturated nitrate solutions, saturated carbonate solutions, saturated phosphate solutions, saturated acetate solutions, or saturated hydroxide solutions of metal ions or ammonium ions; more preferably, the crystallizing material is selected from lithium chloride, lithium bromide, lithium iodide, lithium sulfate, nitrate... At least one of the following: lithium, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, sodium carbonate, sodium nitrate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, sodium hydroxide, potassium chloride, potassium bromide, potassium iodide, potassium sulfate, potassium carbonate, potassium nitrate, potassium dihydrogen phosphate, potassium monohydrogen phosphate, potassium hydroxide, ammonium sulfate, ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium phosphate, magnesium chloride, magnesium nitrate, magnesium acetate, calcium chloride, calcium nitrate, calcium acetate, copper chloride, copper sulfate, copper nitrate, copper acetate, zinc chloride, zinc sulfate, manganese chloride, nickel chloride, ferrous chloride, ferrous sulfate, and ferric chloride;

[0046] The mass ratio of nicosulfuron in the material to be crystallized to the solution containing the crystallizing material is 1:1 to 50; preferably 1:5 to 10; for example, 1:1, 1:3, 1:5, 1:8, 1:10, 1:13, 1:15, 1:18, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, or 1:50.

[0047] While stirring, add the solution of the crystallizing material to the material to be crystallized, or add the material to be crystallized to the solution of the crystallizing material.

[0048] As a preferred embodiment,

[0049] In method b), the solvent evaporation conditions are room temperature to 50°C; preferably 30°C to 40°C, evaporation at atmospheric or reduced pressure; and / or,

[0050] In method c), the grinding time is 20 min to 120 min; preferably 30 min to 60 min; the grinding frequency is 10 Hz to 30 Hz; preferably 20 Hz to 30 Hz.

[0051] The novel crystalline form of nicosulfuron in this invention (essentially a combination of a metal ion or ammonium ion, a nicosulfuron anion, and water) results in different novel crystalline forms depending on the metal ion or ammonium ion bonded to the nicosulfuron anion. Specifically:

[0052] A third aspect of the present invention is to provide a new crystal form 4 of nicotinamide prepared by the method described in the second aspect of the present invention:

[0053] The X-ray powder diffraction pattern of the crystal form, expressed in terms of 2θ diffraction angle, shows characteristic peaks at 13.06, 13.67, 14.80, 18.47, 19.58, and 21.65; the 2θ error range is ±0.2°.

[0054] Preferably, the crystal form also has one or more additional peaks in the X-ray powder diffraction pattern expressed in 2θ diffraction angle at 11.29, 16.99, 18.86, 22.88, 23.47, and 25.09; wherein the 2θ error range is ±0.2°;

[0055] More preferably,

[0056] The crystal form also has one or more additional peaks in the X-ray powder diffraction pattern expressed in 2θ diffraction angle at 12.07, 15.04, 18.08, 20.81, 24.15, and 27.49; wherein the 2θ error range is ±0.2°;

[0057] Even more preferably,

[0058] The crystal form also has one or more additional peaks in the X-ray powder diffraction pattern expressed as 2θ diffraction angle at 7.54, 13.26, 15.52, 17.98, 22.08, 25.42, 26.20, 27.94, 28.57, 29.42, 32.41, and 34.23; wherein the 2θ error range is ±0.2°;

[0059] Even more preferably,

[0060] The X-ray powder diffraction pattern of the crystal form is as follows: Figure 2 As shown.

[0061] A fourth aspect of the present invention is to provide a novel crystalline form 5 of nicotinamide prepared by the method described in the second aspect of the present invention:

[0062] The X-ray powder diffraction pattern of the crystal form, expressed in terms of 2θ diffraction angle, shows characteristic peaks at 12.15, 14.45, 17.57, 19.02, 20.42, and 22.22; the 2θ error range is ±0.2°.

[0063] Preferably, the crystal form also has one or more additional peaks in the X-ray powder diffraction pattern expressed in 2θ diffraction angle at 16.79, 17.79, 21.07, 25.77, 26.48, and 27.61; wherein the 2θ error range is ±0.2°;

[0064] More preferably,

[0065] The crystal form also has one or more additional peaks in the X-ray powder diffraction pattern expressed as 2θ diffraction angle at 8.75, 19.43, 19.68, 22.69, 23.41, 24.37, and 31.71; wherein the 2θ error range is ±0.2°;

[0066] Even more preferably,

[0067] The crystal form also has one or more additional peaks in the X-ray powder diffraction pattern expressed in 2θ diffraction angles at 18.35, 19.90, 24.70, 28.98, 30.24, 31.55, 32.12, 33.60, and 34.81; wherein the 2θ error range is ±0.2°;

[0068] Even more preferably,

[0069] The X-ray powder diffraction pattern of the crystal form is as follows: Figure 3 As shown.

[0070] The fifth aspect of the present invention is to provide a new crystalline form 6 of nicotinamide prepared by the method described in the second aspect of the present invention:

[0071] The X-ray powder diffraction pattern of the crystal form, expressed in terms of 2θ diffraction angle, shows characteristic peaks at 11.05, 13.57, 14.08, 19.35, 20.15, 22.53, and 27.30; the 2θ error range is ±0.2°.

[0072] Preferably, the crystal form also has one or more additional peaks in the X-ray powder diffraction pattern expressed in 2θ diffraction angle at 10.88, 16.13, 22.14, 23.41, 25.05, and 25.62; wherein the 2θ error range is ±0.2°;

[0073] More preferably,

[0074] The crystal form also has one or more additional peaks in the X-ray powder diffraction pattern expressed in 2θ diffraction angle at 11.66, 13.32, 16.46, 21.22, 21.99, 22.83, and 26.03; wherein the 2θ error range is ±0.2°;

[0075] Even more preferably,

[0076] The crystal form also has one or more additional peaks in the X-ray powder diffraction pattern expressed as 2θ diffraction angle at 16.99, 18.80, 20.87, 24.41, 25.23, 26.59, 26.75, 29.62, 33.21, 33.45, 34.97, 36.08, and 36.30; wherein the 2θ error range is ±0.2°;

[0077] Even more preferably,

[0078] The X-ray powder diffraction pattern of the crystal form is as follows: Figure 4 As shown.

[0079] This invention discovers that ammonium ions and nicosulfuron salt form a new crystal form 4.

[0080] This invention discovers that sodium ions and nitrosulfonate form a new crystal form 5.

[0081] This invention discovers that potassium ions and nicosulfuron salt form a new crystal form 6.

[0082] The sixth aspect of the present invention is to provide the use of a salt compound of nicosulfuron as described in the first aspect of the present invention or a new crystal form of nicosulfuron as described in the second aspect of the present invention in pesticides; preferably in herbicides.

[0083] The use of nicosulfuron as a herbicide is well-known in the art and is used on a commercial scale. Furthermore, specific experiments have verified that the novel nicosulfuron crystalline form prepared by this invention has higher chemical stability, resulting in a longer residual effect and better weed control. Therefore, the techniques and uses of nicosulfuron known in the art (e.g., those disclosed in the prior art literature discussed above) can also be applied in a similar manner to the novel nicosulfuron crystalline form of this invention. In summary, the novel nicosulfuron crystalline form described in this invention has the use of controlling weed growth.

[0084] A pesticide composition according to the seventh aspect of the present invention comprises the new crystal form of nicosulfuron according to the third to fifth aspects of the present invention or the salt compound of nicosulfuron according to the first aspect of the present invention.

[0085] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0086] Compared with the prior art, the present invention has the following advantages:

[0087] (1) The new crystal form of nicosulfuron of the present invention has higher chemical stability, longer duration of action, and better inhibitory effect on weed growth.

[0088] (2) The method for preparing the new crystal form of nitrosulfuron of the present invention is simple, low in cost, and suitable for large-scale industrial production. Attached Figure Description

[0089] Figure 1 The powder X-ray diffraction (PXRD) pattern of crystal form 1 of nicosulfuron in the prior art is shown.

[0090] Figure 2 The powder X-ray diffraction (PXRD) pattern of crystal form 4 of nicosulfuron of the present invention is shown.

[0091] Figure 3 The powder X-ray diffraction (PXRD) pattern of crystal form 5 of nicosulfuron of the present invention is shown.

[0092] Figure 4 The powder X-ray diffraction (PXRD) pattern of crystal form 6 of nicosulfuron of the present invention is shown.

[0093] Figure 5 Raman diagram of crystal form 1 of nicosulfuron in the prior art;

[0094] Figure 6 Raman diagram of crystal form 4 of nicosulfuron in this invention;

[0095] Figure 7 Raman diagram of crystal form 5 of nicosulfuron in this invention;

[0096] Figure 8 Raman diagram of crystal form 6 of nicosulfuron in this invention;

[0097] Figure 9 This is a schematic diagram of the asymmetric unit of the crystal structure of nicosulfuron 4 of the present invention;

[0098] Figure 10 This is a schematic diagram of the asymmetric unit of the crystal structure of crystalline form 5 of nicosulfuron of the present invention;

[0099] Figure 11 This is a schematic diagram of the asymmetric unit of the crystal structure of crystalline form 6 of nicosulfuron of the present invention. Detailed Implementation

[0100] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0101] Test method: PXRD (Powder X-ray Diffraction) method: Instrument model: Bruker-D8 ADVANCE, target: Cu-Kα (40kV, 40mA), performed at room temperature using an EIGER2 R detector. The scanning range was in the 2θ interval, from 3° to 40°, and the scanning speed was 10° / min.

[0102] Measurement discrepancies associated with these powder X-ray diffraction analysis results are caused by a variety of factors, including: (a) errors in sample preparation (e.g., sample height), (b) instrument errors, (c) calibration discrepancies, (d) operator errors (including errors occurring when determining peak positions), and (e) the properties of the material (e.g., preferred orientation errors). Calibration errors and sample height errors often result in shifts in the same direction for all peaks. When using a flat support, small differences in sample height can lead to large shifts in XRD peak positions. Systematic studies have shown that a 1 mm sample height difference can result in peak shifts as high as 1° 2θ. These shifts can be identified from the X-ray diffraction pattern and can be eliminated by compensating for the shifts (applying a systematic calibration factor to all peak position values) or by recalibrating the instrument. As mentioned above, measurement errors from different instruments can be corrected by applying a systematic calibration factor to ensure consistent peak positions.

[0103] Raman spectroscopy method: Using a Raman spectroscopy microscope (XploRA PLUS, HORIBA, France) at 200-1800 cm⁻¹ -1 Raman spectra were collected within a certain range. A 532 nm laser was selected, and the laser spot on the sample was focused to ~1.1 μm using a 50x zoom lens. The sample was analyzed directly on a glass slide using a 100 mW laser power and a 50 μm pinhole spectrometer aperture.

[0104] The water used in the examples was all high-purity water; all other reagents were of analytical grade.

[0105] The nicosulfuron used in this embodiment of the invention is a commercially available crystal form 1 product purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd., and is of analytical grade; the powder X-ray diffraction (PXRD) pattern of crystal form 1 of nicosulfuron in the prior art is shown below. Figure 1 The Raman diagram of crystal form 1 of nicosulfuron in the prior art is shown below. Figure 5 .

[0106] Example 1

[0107] Preparation of crystal form 4:

[0108] Take 1g of nicosulfuron, add 10mL of water, and under sonication, add 1mL of ammonia (25wt%) until the nicosulfuron is completely dissolved. Filter the filtrate into a 25mL glass bottle as the mother liquor. Slowly add 10mL of saturated ammonium chloride solution dropwise to the mother liquor while stirring. A yellow solid precipitates. After stirring for 15 minutes, filter under vacuum and wash with an appropriate amount of saturated ammonium chloride solution to obtain a loose, bright yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0109] The PXRD pattern of the obtained crystal form 4 is shown in the figure. Figure 2 The diffraction angle data are shown in Table 1 below; the Raman diagram of the obtained crystal form 4 is shown in Table 1 below. Figure 6 .

[0110] Table 1. PXRD data for crystal form 4

[0111]

[0112] Example 2

[0113] Preparation of crystal form 4:

[0114] Take 1g of nicosulfuron, add 15mL of water, and under sonication, add 2mL (25wt%) of ammonia until the nicosulfuron is completely dissolved to obtain a nicosulfuron mother liquor. Take 15mL of saturated ammonium chloride solution in a bottle, and slowly filter the mother liquor into the saturated ammonium chloride solution while stirring. A yellow solid precipitates out. After stirring for 15 minutes, filter under vacuum and wash with an appropriate amount of saturated ammonium chloride solution to obtain a loose, bright yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0115] Example 3

[0116] Preparation of crystal form 4:

[0117] Take 1g of mesotrione, add 10mL of water, add 1mL (25wt%) of ammonia under sonication until mesotrione is completely dissolved, filter, concentrate under reduced pressure to dryness, and obtain a bright yellow powder.

[0118] Example 4

[0119] Preparation of crystal form 4:

[0120] Dissolve 1g of mesotrione in 10mL of acetonitrile, then add 3mL (25wt%) ammonia and allow it to evaporate slowly at room temperature. As the solvent evaporates, transparent pale yellow crystals precipitate in the flask. Filter the solution and dry the resulting solid under vacuum at 45°C for 8 hours to obtain a yellow crystalline product.

[0121] Example 5

[0122] Preparation of crystal form 4:

[0123] Dissolve 1g of mesotrione in 20mL of acetone, then add 1mL (25wt%) of ammonia and allow it to evaporate slowly at room temperature. As the solvent evaporates, transparent pale yellow crystals precipitate in the flask. Filter the solution and dry the resulting solid under vacuum at 40°C for 8 hours to obtain a yellow crystalline product.

[0124] Example 6

[0125] Preparation of crystal form 4:

[0126] Weigh 90 mg of mesotrione into a 2 mL centrifuge tube, add one medium-sized steel ball, add 25 μL (25 wt%) of ammonia water, and grind in a ball mill for 30 minutes. After grinding, remove and let stand for 2 hours, scrape off the solid, and vacuum dry at 35 °C for 8 hours to obtain a yellow powdery crystalline product.

[0127] Example 7

[0128] Preparation of crystal form 5:

[0129] Take 1g of commercially available mesotrione, add 12mL of water, and slowly add 1mL of 25wt% sodium hydroxide solution dropwise under sonication to dissolve the solid. Filter into a 25mL single-necked flask. Add 4mL of saturated sodium dihydrogen phosphate solution (pH of the crystallization system is approximately 5) dropwise while stirring, precipitating the solid. After stirring for 20 minutes, filter under vacuum and wash with saturated sodium chloride solution to obtain a loose, pale yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a pale yellow powdery crystalline product.

[0130] The PXRD pattern of the obtained crystal form 5 is shown in the figure. Figure 3 The diffraction angle data are shown in Table 2 below; the Raman diagram of the obtained crystal form 5 is shown in Table 2. Figure 7 .

[0131] Table 2. PXRD data for crystal form 5

[0132]

[0133]

[0134] Example 8

[0135] Preparation of crystal form 5:

[0136] Take 1g of commercially available nicosulfuron and add it to 20mL of water. Slowly add 2mL of 25wt% sodium hydroxide solution under sonication to dissolve the solid, obtaining a nicosulfuron mother liquor. Take 10mL of saturated sodium dihydrogen phosphate solution in a glass bottle and slowly filter the mother liquor into the solution while stirring. A solid precipitates out. After stirring for 20 minutes, filter under vacuum and wash with saturated sodium chloride solution to obtain a loose, pale yellow solid. Dry under vacuum at 40℃ for 10 hours to obtain a pale yellow powdery crystalline product.

[0137] Example 9

[0138] Preparation of crystal form 5:

[0139] Take 1g of mesotrione, add 10mL of acetonitrile, and then add 2mL of 1wt% sodium hydroxide solution. The solid dissolves and slowly evaporates at room temperature. As the solvent evaporates, transparent pale yellow crystals precipitate in the flask. Then filter and dry the obtained solid under vacuum at 45℃ for 8 hours to obtain a pale yellow crystalline product.

[0140] Example 10

[0141] Preparation of crystal form 5:

[0142] Dissolve 1g of mesotrione in 20mL of methanol, then add 300µL of 10wt% sodium hydroxide solution until the solid dissolves. Allow the solution to evaporate slowly at room temperature. As the solvent evaporates, transparent pale yellow crystals precipitate in the flask. Filter the solution and dry the resulting solid under vacuum at 40°C for 8 hours to obtain a pale yellow crystalline product.

[0143] Example 11

[0144] Preparation of crystal form 5:

[0145] Weigh 11 mg of sodium hydroxide and 90 mg of mesotrione into a 2 mL centrifuge tube, add one medium-sized steel ball and 20 μL of water, and grind in a ball mill for 30 minutes. After grinding, remove and let stand for 2 hours, scrape off the solid, and vacuum dry at 35 °C for 8 hours to obtain a pale yellow powdery crystalline product.

[0146] Example 12

[0147] Preparation of crystal form 6:

[0148] Take 1g of mesotrione and 1.5g of potassium hydroxide, add 16mL of water until the solid is completely dissolved, and filter into a 25mL glass bottle as the mother liquor. Slowly add the saturated potassium hydroxide solution dropwise to the mesotrione mother liquor while stirring, and a yellow solid precipitates out. After 10 minutes, filter under vacuum and dry at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0149] The PXRD pattern of the obtained crystal form 6 is shown in the figure. Figure 4 The diffraction angle data are shown in Table 3 below; the Raman diagram of the obtained crystal form 6 is shown in Table 3 below. Figure 8 .

[0150] Table 3. PXRD data for crystal form 6

[0151]

[0152]

[0153] Example 13

[0154] Preparation of crystal form 6:

[0155] Take 1g of mesotrione and 2g of potassium hydroxide, add 20mL of water until the solid is completely dissolved to prepare mesotrione mother liquor. Slowly filter the mother liquor into a saturated potassium hydroxide solution while stirring, and a yellow solid precipitates out. After 10 minutes, filter under vacuum and dry at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0156] Example 14

[0157] Preparation of crystal form 6:

[0158] Dissolve 1g of mesotrione in 10mL of acetonitrile, then add 1% potassium hydroxide solution until the solid dissolves. Allow the solution to evaporate slowly at room temperature. As the solvent evaporates, transparent yellow crystals precipitate in the flask. Filter the solution and dry the resulting solid under vacuum at 45°C for 8 hours to obtain a yellow crystalline product.

[0159] Example 15

[0160] Preparation of crystal form 6:

[0161] Dissolve 1g of mesotrione in 20mL of methanol, then add 5% potassium hydroxide solution until the solid dissolves. Allow the solution to evaporate slowly at room temperature. As the solvent evaporates, transparent yellow crystals precipitate in the flask. Filter the solution and dry the resulting solid under vacuum at 40°C for 8 hours to obtain a yellow crystalline product.

[0162] Example 16

[0163] Preparation of crystal form 6:

[0164] Weigh 15 mg of potassium hydroxide and 90 mg of mesotrione into a 2 mL centrifuge tube, add one medium-sized steel ball and 20 μL of water, and grind in a ball mill for 30 minutes. After grinding, remove and let stand for 2 hours, scrape off the solid, and vacuum dry at 35 °C for 8 hours to obtain a yellow powdery crystalline product.

[0165] Example 17

[0166] Preparation of crystal form 4:

[0167] Take 1g of mesotrione, add 5mL of water, and slowly add 0.5mL of 25wt% sodium hydroxide solution dropwise under sonication to dissolve the solid. Filter into a 25mL single-necked flask. Add 5mL of saturated ammonium sulfate solution dropwise while stirring, and the solid precipitates. After stirring for 30 minutes, filter under vacuum and wash with saturated ammonium sulfate solution to obtain a loose yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0168] Example 18

[0169] Preparation of crystal form 4:

[0170] Take 1g of nicosulfuron and 200mg of potassium hydroxide, add 15mL of water until the solid is completely dissolved to prepare nicosulfuron mother liquor. Slowly filter the mother liquor into 10mL of saturated ammonium sulfate solution with stirring, and a yellow solid precipitates. After 10 minutes, filter under vacuum and dry at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0171] Example 19

[0172] Preparation of crystal form 4:

[0173] Take 1g of nicosulfuron and 200mg of sodium carbonate, add 15mL of water until the solid is completely dissolved to prepare nicosulfuron mother liquor. Slowly filter the mother liquor into 10mL of saturated ammonium sulfate solution with stirring, and a yellow solid precipitates out. After 10 minutes, filter under vacuum and dry at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0174] In Examples 17-19 of this invention, the amount of alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate added is very small, mainly to increase the solubility of nicosulfuron. The crystal form precipitated in this invention depends on the large number of ions in the large amount of solution used in the crystallization stage.

[0175] Example 20

[0176] Preparation of crystal form 5:

[0177] Take 1g of mesotrione, add 10mL of water, and slowly add 1mL of 10wt% sodium carbonate solution dropwise under sonication to dissolve the solid. Filter into a 25mL single-necked flask. Add 4mL of saturated sodium carbonate solution dropwise while stirring, and the solid precipitates. After stirring for 30 minutes, filter under vacuum and wash with saturated sodium carbonate solution to obtain a loose yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0178] Example 21

[0179] Preparation of crystal form 5:

[0180] Take 1g of nicosulfuron and 400mg of sodium bicarbonate, add 20mL of water until the solid is completely dissolved to prepare nicosulfuron mother liquor. Slowly filter the mother liquor into a saturated sodium dihydrogen phosphate solution with stirring, and a yellow solid precipitates out. After 10 minutes, filter under vacuum and dry at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0181] Example 22

[0182] Preparation of crystal form 5:

[0183] Take 1g of mesotrione, add 12mL of water, and slowly add 1mL of 25wt% sodium phosphate solution dropwise under sonication to dissolve the solid. Filter into a 25mL single-necked flask. Add 6mL of saturated sodium sulfate solution dropwise while stirring, and the solid precipitates. After stirring for 30 minutes, filter under vacuum and wash with saturated sodium sulfate solution to obtain a loose yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0184] Example 23

[0185] Preparation of crystal form 5:

[0186] Take 1g of mesotrione and 400mg of lithium hydroxide, add 10mL of water until the solid is completely dissolved to prepare mesotrione mother liquor. Slowly filter the mother liquor into a saturated sodium chloride solution with stirring, and a yellow solid precipitates out. After 10 minutes, filter under vacuum and dry at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0187] Example 24

[0188] Preparation of crystal form 5:

[0189] Take 1g of mesotrione, add 12mL of water, and slowly add 1mL of 25wt% sodium carbonate solution dropwise under sonication to dissolve the solid. Filter into a 25mL single-necked flask. Add 1mol / L hydrochloric acid dropwise with stirring until the pH is 4-6. Evaporate the solution at 30℃ until the solid precipitates. Filter under vacuum to obtain a loose yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0190] Example 25

[0191] Preparation of crystal form 5:

[0192] Weigh 15 mg of sodium carbonate and 90 mg of mesotrione into a 2 mL centrifuge tube, add one medium-sized steel ball and 20 μL of water, and grind in a ball mill for 30 minutes. After grinding, remove and let stand for 2 hours, scrape off the solid, and vacuum dry at 35 °C for 8 hours to obtain a yellow powdery crystalline product.

[0193] Example 26

[0194] Preparation of crystal form 6:

[0195] Take 1g of mesotrione, add 12mL of water, and slowly add 1mL of 40wt% potassium hydroxide solution dropwise under sonication to dissolve the solid. Filter into a 25mL single-necked flask. Add 4mL of saturated potassium chloride solution dropwise while stirring, and the solid precipitates. After stirring for 30 minutes, filter under vacuum and wash with saturated potassium chloride solution to obtain a loose yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0196] Example 27

[0197] Preparation of crystal form 6:

[0198] Take 1g of nicosulfuron and 2g of potassium carbonate, add 20mL of water until the solid is completely dissolved to prepare nicosulfuron mother liquor. Slowly filter the mother liquor into a saturated potassium carbonate solution while stirring, and a yellow solid precipitates out. After 10 minutes, filter under vacuum and dry at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0199] Example 28

[0200] Preparation of crystal form 6:

[0201] Take 1g of mesotrione, add 12mL of water, and slowly add 1mL of 20wt% potassium phosphate solution dropwise under sonication to dissolve the solid. Filter into a 25mL single-necked flask. Add 4mL of saturated potassium dihydrogen phosphate solution dropwise while stirring, and the solid precipitates. After stirring for 30 minutes, filter under vacuum and wash with saturated potassium dihydrogen phosphate solution to obtain a loose yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0202] Example 29

[0203] Preparation of crystal form 6:

[0204] Take 1g of nicosulfuron and 4g of potassium bicarbonate, add 20mL of water until the solid is completely dissolved to prepare nicosulfuron mother liquor. Slowly filter the mother liquor into a saturated potassium chloride solution with stirring, and a yellow solid precipitates out. After 10 minutes, filter under vacuum and dry at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0205] Example 30

[0206] Preparation of crystal form 6:

[0207] Take 1g of mesotrione, add 12mL of water, and slowly add 1mL of 30wt% potassium carbonate solution dropwise under sonication to dissolve the solid. Filter into a 25mL single-necked flask. Add 4mL of saturated potassium hydroxide solution dropwise while stirring, and the solid precipitates. After stirring for 30 minutes, filter under vacuum and wash with saturated potassium hydroxide solution to obtain a loose yellow solid. Dry under vacuum at 35℃ for 8 hours to obtain a yellow powdery crystalline product.

[0208] Example 31

[0209] Preparation of crystal form 6:

[0210] Weigh 19 mg of potassium carbonate and 90 mg of mesotrione into a 2 mL centrifuge tube, add one medium-sized steel ball and 20 μL of water, and grind in a ball mill for 30 minutes. After grinding, remove and let stand for 2 hours, scrape off the solid, and vacuum dry at 35 °C for 8 hours to obtain a yellow powdery crystalline product.

[0211] Example 32

[0212] Photolysis of suspension:

[0213] This invention provides a comparison of the decomposition effects of methyl oleate suspensions of different crystalline forms of nicosulfuron under 500W xenon lamp irradiation, demonstrating the high chemical stability of the novel crystalline form. Specifically, this is demonstrated by the state of the suspensions after continuous irradiation for a certain period and the residual amount of nicosulfuron in the suspensions, as follows:

[0214] 1. Experimental Samples:

[0215] Commercially available nicosulfuron crystal form 1, and crystal forms 4, 5, and 6 prepared according to Examples 1, 7, and 12 above.

[0216] 2. Suspension preparation:

[0217] Weigh approximately 10 mg of the above experimental sample using an analytical balance (0.00001 g), place it in a 2 mL transparent glass bottle, add 1.5 mL of methyl oleate, add a magnetic stir bar, and sonicate until homogeneous to obtain a suspension of mesotrione.

[0218] 3. Experimental methods:

[0219] Four groups of suspensions were placed in a photoreaction apparatus, magnetic stirring was turned on, and after 96 hours of light exposure, color changes were recorded. The content of mesotrione was determined by high-performance liquid chromatography using a reversed-phase column and eluent.

[0220] 4. Experimental Results:

[0221] Table 4 shows the changes in the four crystalline suspensions after 96 hours of light exposure. Crystallization 1 exhibited the highest photolysis rate (36.68%) and the largest color change, becoming the darkest after light exposure, indicating poor stability. Crystallization 4, 5, and 6 of the nicosulfuron of this invention showed significant improvements in stability, with decreased photolysis rates and smaller color changes. Crystallization 5 showed the best effect; after light exposure, the suspension color remained essentially unchanged, and it had the lowest photolysis rate (0.04%), demonstrating extremely strong stability.

[0222] Photolysis efficiency (%) = (Content before illumination - Content after illumination) / Content before illumination * 100%

[0223] Table 4. Decomposition rate of nicosulfuron after 96 hours of light exposure

[0224]

[0225] The experimental results show that, in oil suspensions, the crystal forms 4, 5, and 6 of nicosulfuron of the present invention all exhibit better photodegradation stability (i.e., better photothermal stability) compared to the commercially available crystal form 1. Among them, crystal form 5 exhibits the highest chemical stability, with a photolysis rate of only 0.04%, significantly higher than the 36.68% of crystal form 1, and its color remains essentially unchanged. Therefore, the crystal form stability of nicosulfuron of the present invention is better than that of crystal form 1.

[0226] Example 33

[0227] Indoor bioactivity assay:

[0228] This invention provides a comparative study of the application and effects of different solid forms of nicosulfuron in controlling weed growth in indoor environments, demonstrating the high activity of the novel crystalline form. Specifically, the control effect of each crystalline form on velvetleaf was investigated using a foliar spray method, with the following steps:

[0229] 1. Experimental Samples:

[0230] Commercially available nicosulfuron crystal form 1, and crystal forms 4, 5, and 6 prepared according to Examples 1, 7, and 12 above.

[0231] 2. Compound preparation:

[0232] Weigh out a certain mass of the above experimental samples using an analytical balance (0.00001 g). Dissolve the original drug in a small amount of solvent, and then prepare the test solution of the required concentration using a 1‰ Tween 80 solution.

[0233] 3. Experimental methods:

[0234] A fixed amount of velvetleaf seeds were sown in an area with a cross-sectional area of ​​100 cm². 2 After sowing in culture pots, cover with 1cm of soil, compact, water, and then cultivate in a greenhouse using conventional methods. Once the weeds have grown to the 2-leaf stage, select uniformly growing test materials and perform foliar spraying using a tracked crop sprayer (designed and manufactured by Engineer Research Ltd., UK) (spraying pressure 1.95kg / cm²). 2 Spray volume 50mL / m 2The track speed was 30 cm / s, and the nozzle was a fan-shaped nozzle. A 1‰ Tween 80 solution was used as a control. After treatment, the samples were left to stand until the herbicide solution air-dried naturally. Then, they were placed in a greenhouse and managed using standard methods, with bottom irrigation to prevent the solution from being washed away. Twenty-one days after treatment, the symptoms and severity of damage to velvetleaf were visually assessed to evaluate the herbicidal activity of the herbicide.

[0235] 4. Experimental Results:

[0236] Table 5 shows the results of different treatment groups inhibiting the growth of Abutilon theophrasti var. mongolica 21 days after drug administration.

[0237] Growth inhibition rate = (Fresh weight of aboveground parts in control group - Fresh weight of aboveground parts in treatment group) / Fresh weight of aboveground parts in control group * 100%

[0238] Table 5. Results of growth inhibition assays for different treatment groups of Abutilon theophrasti

[0239]

[0240] The experimental results show that the crystalline forms 4, 5, and 6 of nicosulfuron of this invention exhibit better herbicidal activity than the commercially available crystalline form 1 at different dosages. Specifically, when crystalline form 1 was applied at 37.5 g / ha, the growth inhibition rate of velvetleaf was only 70%, while the control efficacy of crystalline forms 4, 5, and 6 of nicosulfuron was 100% at this dosage. Crystalline form 5 showed the highest activity, maintaining a 90% control efficacy against velvetleaf at 9.375 g / ha, while the control efficacy of the commercially available crystalline form 1 was 0 at this dosage, demonstrating superior herbicidal activity.

[0241] In summary, this invention, starting from the compound nicosulfuron itself, screened and developed a series of superior nicosulfuron crystal forms with stronger chemical stability. These crystal forms enhance resistance to decomposition and improve biological activity, thereby achieving reduced dosage and increased efficiency of nicosulfuron, which has great application potential.

[0242] Single crystal tests were performed on commercially available nicosulfanilamide crystal form 1, and crystal forms 4, 5, and 6 prepared according to Examples 1, 7, and 12 above. The results are shown in Table 6 below. Figure 9 , Figure 10 as well as Figure 11 As shown.

[0243] Table 6 Single-crystal diffraction data for each crystal form

[0244]

[0245]

[0246] The molecular formula of crystal form 1 can be seen from the single crystal structure as C. 14 H 13NO7S.

[0247] From the data of single crystal structure and Figure 9 As can be seen from the data, in crystal form 4, the nicosulfuron molecule exists as a dehydrogenated anion, with a ratio of ammonium ion to nicosulfuron anion of 1:1, which can be represented as NH4+. + (C 14 H 12 NO7S) - .

[0248] From the data of single crystal structure and Figure 10 From the data, it can be seen that in crystal form 5, the nicosulfuron molecule exists in the form of a dehydrogenated anion, and the ratio of sodium ions, nicosulfuron anions, and water molecules is 1:1:1, which can be represented as Na + (C 14 H 12 NO7S) -. H2O.

[0249] From the data of single crystal structure and Figure 11 From the data, it can be seen that in crystal form 6, the nicosulfuron molecule exists in the form of a dehydrogenated anion. The ratio of potassium ions, nicosulfuron anions, and water molecules is 1:1:0.5, which can be represented as K + (C 14 H 12 NO7S) -. 0.5H2O.

[0250] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

[0251] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0252] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0253] In the context of this specification, except where expressly stated otherwise, any matters or issues not mentioned shall apply directly to those known in the art without any modification.

Claims

1. A salt compound of mesotrione, characterized by, The structural formula of the salt compound of mesotrione is as follows: Wherein, n is 0-3; m is 0-3; M n+ is a monovalent metal ion, a divalent metal ion, a trivalent metal ion or an ammonium ion; Preferably, The monovalent metal ion is lithium ion, sodium ion or potassium ion; and / or, The divalent metal ion is magnesium ion, calcium ion, copper ion, zinc ion, manganese ion, ferrous ion or nickel ion; and / or, The trivalent metal ion is iron ion.

2. A process for preparing a new crystalline form of mesotrione characterized in that, Comprising the following steps: (1) mixing mesotrione, alkaline substance and solvent to obtain crystallization material; (2) crystallizing the crystallization material to obtain the new crystal form of mesotrione; The pH value of the crystallization system is greater than or equal to 4.

3. The preparation method of the new crystal form of mesotrione according to claim 2, characterized in that: Step (1), The alkaline substance is selected from at least one of the following: salt corresponding to the metal element, oxide corresponding to the metal element, hydroxide corresponding to the metal element, ammonia, ammonia water or ammonium salt; preferably, the alkaline substance is selected from at least one of the following: sodium salt, sodium hydroxide, potassium salt, potassium hydroxide, lithium salt, lithium hydroxide, ammonia, ammonia water or ammonium salt; and / or, The solvent is selected from at least one of the following: ketone, alcohol, nitrile, amide, ester, halogenated alkane, dimethyl sulfoxide or water; preferably, the solvent is selected from at least one of the following: ketone, alcohol, nitrile, amide, dimethyl sulfoxide or water; Preferably, The sodium salt is selected from at least one of the following: sodium acetate, sodium phosphate, monosodium phosphate, sodium carbonate or sodium bicarbonate; and / or, The potassium salt is selected from at least one of the following: potassium acetate, potassium phosphate, monopotassium phosphate, potassium carbonate or potassium bicarbonate; and / or, The lithium salt is selected from at least one of the following: lithium acetate, lithium phosphate, monolithium phosphate, lithium carbonate or lithium bicarbonate; and / or, The ammonium salt is selected from at least one of the following: ammonium acetate, ammonium phosphate, monammonium phosphate, ammonium carbonate or ammonium bicarbonate.

4. The preparation method of the new crystal form of mesotrione according to claim 2, characterized in that: Step (1), The molar ratio of mesotrione to metal ion or ammonium ion in the alkaline substance is 1:0.3-20; preferably, 1:0.3-1.1 or 1:2-20; Preferably, the alkaline substance is added in the form of an alkaline substance solution, and the concentration of the alkaline substance solution is 5wt%-50wt%.

5. The preparation method of the new crystal form of mesotrione according to claim 2, characterized in that: Step (2), the crystallization method is selected from at least one of the following methods: Method a) mixing the crystallization material and a solution containing crystallization material to precipitate the new crystal form of mesotrione; preferably, the crystallization material is selected from at least one of the following: salt or hydroxide of metal element or ammonium ion; preferably, the concentration of the solution containing crystallization material is more than 25% of the saturated solution concentration of the crystallization material; Method b) evaporating the solvent in the crystallization material to precipitate the new crystal form of mesotrione; Method c) grinding the crystallization material to precipitate the new crystal form of mesotrione; Preferably, In method a), the crystallization material is selected from at least one of a halide, a sulfate, a nitrate, a carbonate, a phosphate, an acetate or a hydroxide of a metal ion or an ammonium ion; preferably, the solution containing the crystallization material is selected from at least one of a saturated halide solution, a saturated sulfate solution, a saturated nitrate solution, a saturated carbonate solution, a saturated phosphate solution, a saturated acetate solution or a saturated hydroxide solution of a metal ion or an ammonium ion; the mass ratio of the mesotrione in the material to be crystallized to the solution containing the crystallization material is 1:1 to 50; preferably 1:5 to 10; and / or, the solution of the crystallization material is added to the material to be crystallized or the material to be crystallized is added to the solution of the crystallization material under stirring. In method b), the solvent evaporation is performed at a temperature of from room temperature to 50°C; preferably from 30°C to 40°C; and / or, In method c), the grinding is performed for a time of from 20 min to 120 min; preferably from 30 min to 60 min; and at a frequency of from 10 Hz to 30 Hz; preferably from 20 Hz to 30 Hz.

6. A new crystalline form 4 of mesotrione prepared according to the method of any one of claims 2 to 5, characterized in that: the X-ray powder diffraction pattern expressed in terms of 2Θ diffraction angles shows characteristic peaks at 13.06, 13.67, 14.80, 18.47, 19.58, 21.65; wherein the error range of 2Θ is ±0.2°; preferably, the crystalline form further has one or more additional peaks expressed in terms of 2Θ diffraction angles at 11.29, 16.99, 18.86, 22.88, 23.47, 25.09; wherein the error range of 2Θ is ±0.2°; further preferably, the crystalline form further has one or more additional peaks expressed in terms of 2Θ diffraction angles at 12.07, 15.04, 18.08, 20.81, 24.15, 27.49; wherein the error range of 2Θ is ±0.2°; still further preferably, the crystalline form further has one or more additional peaks expressed in terms of 2Θ diffraction angles at 7.54, 13.26, 15.52, 17.98, 22.08, 25.42, 26.20, 27.94, 28.57, 29.42, 32.41, 34.23; wherein the error range of 2Θ is ±0.2°; still further preferably, the X-ray powder diffraction pattern of the crystalline form is shown in Figure 2.

7. A new crystalline form 5 of mesotrione prepared according to the method of any one of claims 2 to 5, characterized in that: the X-ray powder diffraction pattern expressed in terms of 2Θ diffraction angles shows characteristic peaks at 12.15, 14.45, 17.57, 19.02, 20.42, 22.22; wherein the error range of 2Θ is ±0.2°; Preferably, the crystal form further has one or more additional peaks in an X-ray powder diffraction pattern expressed in terms of 2θ diffraction angles at 16.79, 17.79, 21.07, 25.77, 26.48, 27.61; wherein the error range of the 2θ is ±0.2°; Further preferably, the crystal form further has one or more additional peaks in an X-ray powder diffraction pattern expressed in terms of 2θ diffraction angles at 8.75, 19.43, 19.68, 22.69, 23.41, 24.37, 31.71; wherein the error range of the 2θ is ±0.2°; Still further preferably, the crystal form further has one or more additional peaks in an X-ray powder diffraction pattern expressed in terms of 2θ diffraction angles at 18.35, 19.90, 24.70, 28.98, 30.24, 31.55, 32.12, 33.60, 34.81; wherein the error range of the 2θ is ±0.2°; Still further preferably, the crystal form further has one or more additional peaks in an X-ray powder diffraction pattern expressed in terms of 2θ diffraction angles at 16.99, 18.80, 20.87, 24.41, 25.23, 26.59, 26.75, 29.62, 33.21, 33.45, 34.97, 36.08, 36.30; wherein the error range of the 2θ is ±0.2°; Still further preferably, the X-ray powder diffraction pattern of the crystal form is shown in Figure 4.

8. The new crystal form 6 of mesotrione prepared according to the method of any one of claims 2-5, characterized in that: the crystal form has characteristic peaks in an X-ray powder diffraction pattern expressed in terms of 2θ diffraction angles at 11.05, 13.57, 14.08, 19.35, 20.15, 22.53, 27.30; wherein the error range of the 2θ is ±0.2°; Preferably, the crystal form further has one or more additional peaks in an X-ray powder diffraction pattern expressed in terms of 2θ diffraction angles at 10.88, 16.13, 22.14, 23.41, 25.05, 25.62; wherein the error range of the 2θ is ±0.2°; Further preferably, the crystal form further has one or more additional peaks in an X-ray powder diffraction pattern expressed in terms of 2θ diffraction angles at 11.66, 13.32, 16.46, 21.22, 21.99, 22.83, 26.03; wherein the error range of the 2θ is ±0.2°; Still further preferably, the crystal form further has one or more additional peaks in an X-ray powder diffraction pattern expressed in terms of 2θ diffraction angles at 16.99, 18.80, 20.87, 24.41, 25.23, 26.59, 26.75, 29.62, 33.21, 33.45, 34.97, 36.08, 36.30; wherein the error range of the 2θ is ±0.2°; Still further preferably, 10. A pesticidal composition, characterized by, the X-ray powder diffraction pattern of the crystal form is shown in Figure 4.

9. Use of the salt compound of mesotrione according to claim 1 or the new crystal form of mesotrione according to any one of claims 6-8 in a pesticide; preferably in a herbicide. The new crystal form of mesotrione according to any one of claims 6-8 or the salt compound of mesotrione according to claim 1.

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