Novel crystal form of cyantraniliprole and method of preparation and use thereof

Abstract

The application discloses a new crystal form of brofenvalerate, a preparation method and application thereof. The new crystal form of brofenvalerate comprises a powder X-ray diffraction spectrum expressed by 2θ±0.2° diffraction angle, and the powder X-ray diffraction spectrum shows characteristic peaks at 8.70, 9.94, 11.24, 12.24, 22.38 and 24.70. Compared with the existing crystal form of brofenvalerate, the new crystal form of brofenvalerate discovered by the application has a simple preparation method, more excellent properties and higher biological activity, and can be used for the prevention and control of pests of the orders Lepidoptera, Hemiptera, Coleoptera, Thysanoptera, Hymenoptera, Acarina and Diptera.

Description

Technical Field

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

[0002] Cyanobacterium oxychloride, also known as cyananthramide, has the chemical name 3-bromo-1-(3-chloro-2-pyridyl)-N-[4-cyano-2-methyl-6-[(methylamino)-carbonyl]phenyl]-1H-pyrazole-5-carboxamide. It is the second diamide insecticide developed by DuPont after chlorantraniliprole. As a ryanodine receptor inhibitor, it has a broad insecticidal spectrum, exhibiting both stomach poison and contact action. Its molecular formula is C1... 19 H 14 BrClN6O2 has the following chemical structure:

[0003]

[0004] Polymorphism refers to the phenomenon that a substance can exist in two or more different crystal structures, also known as polymorphism or isomorphism. The emergence of polymorphism is a result of kinetic competition during crystallization thermodynamics and molecular recognition, and is greatly affected by changes in crystallization conditions, such as solvent composition, temperature, concentration, supersaturation, pH, stirring speed, and impurity content. Generally, a compound will exist in multiple crystal forms, and the physicochemical properties and biological activities of these crystal forms will differ; therefore, screening for the dominant crystal form is very important.

[0005] PCT patent WO2004067528A1 discloses a method for preparing 3-bromo-1-(3-chloro-2-pyridyl)-N-[4-cyano-2-methyl-6[(methylamino)-carbonyl]phenyl]-1H-pyrazole-5-carboxamide and its application as an insecticide. Chinese patent CN 102216284 B studied the conversion of bromocyanamide with its hydrate; however, due to the variation in water content of the hydrate with air humidity, its biological activity was not investigated in depth. The patent mentions that the non-crystalline powder X-ray diffraction pattern recorded by Cu-Kα radiation shows diffraction angles of 2θ±0.2° at 6.78, 11.09, 11.82, 13.90, 14.76, 15.42, 15.73, 16.61, 18.55, 18.89, 19.31, 19.94, 20.99, 22.01, 22.53, 23.60, 24.14, 24.44, and 24. Characteristic peaks are observed at 89, 26.03, 26.57, 26.98, 27.59, 28.70, 29.27, 29.96, 31.04, 31.52, 32.13, 32.59, 33.30, 33.86, 34.64, 35.21, 36.02, 36.32, 36.98, 38.03, 38.42, 39.44, and 39.77 (for ease of description, this is referred to as crystal form I). Chinese patent CN 116490492A explored the solid form of bromocyanamide, disclosing three new crystal forms C, D (crystal form I in this paper), and F, as well as their preparation methods. Reproducing the preparation process revealed that crystal forms C and F are solvates, and due to stability issues, they are unsuitable for formulation development.

[0006] The insecticidal effect of the existing crystalline form I of bromocyanamide is generally limited and needs to be improved. Other crystalline forms (crystalline form C, crystalline form D, and hydrated crystalline form) have stability issues and are not suitable for large-scale development. Therefore, it is necessary to develop new crystalline forms of bromocyanamide to meet the needs of actual production and use. Summary of the Invention

[0007] To address the problems existing in the prior art, this invention proposes a new crystalline form of bromocyanamide, its preparation method, and its applications. This invention develops a new crystalline form of bromocyanamide with superior properties and higher bioactivity.

[0008] One objective of this invention is to provide a novel crystalline form of bromocyanamide, wherein the crystalline form comprises a powder X-ray diffraction pattern with characteristic peaks at 8.70, 9.94, 11.24, 12.24, 22.38, and 24.70, expressed as a diffraction angle of 2θ ± 0.2°.

[0009] In a preferred embodiment, the crystal form also has one or more additional peaks at 20.20, 20.74, 22.14, 23.54, 24.70, and 25.18 in the powder X-ray diffraction pattern expressed as 2θ±0.2° diffraction angle;

[0010] Preferably,

[0011] The crystal form also has one or more additional peaks at 10.72, 11.82, 16.02, 21.38, 22.68, 26.06, and 29.50 in the powder X-ray diffraction pattern expressed as 2θ±0.2° diffraction angle;

[0012] More preferably,

[0013] The crystal form also has one or more additional peaks in its powder X-ray diffraction pattern, expressed as a diffraction angle of 2θ ± 0.2°, at 13.78, 14.16, 14.62, 16.56, 17.44, 24.32, 27.00, 27.24, 27.66, 28.08, 28.64, 28.92, 30.22, 30.60, 30.94, 31.82, 32.56, 33.10, 34.10, 34.62, 35.38, 36.14, 36.54, 37.16, 38.24, and 38.94.

[0014] Even more preferably,

[0015] The powder X-ray diffraction pattern of the crystal form is as follows: Figure 2 As shown.

[0016] A second objective of this invention is to provide a method for preparing a new crystal form of bromocyanamide as described in one objective of this invention, comprising one of the following methods:

[0017] Method 1:

[0018] (1) Mix bromocyanamide with a solvent to obtain a mixture;

[0019] (2) Add additives to the mixture, then crystallize, separate solids and liquids, wash, and obtain a new crystal form of bromocyanamide;

[0020] In this invention, the above mixture can be a homogeneous solution or a suspension, depending on whether bromocyanamide can be completely dissolved in the solvent;

[0021] or,

[0022] Method 2:

[0023] (1) After heating bromocyanamide and a high-boiling-point compound together until completely melted, a melt is obtained; the boiling point of the high-boiling-point compound is ≥80℃;

[0024] (2) Additives are added to the melt, and then the melt is crystallized to obtain a new crystal form of bromocyanamide;

[0025] or,

[0026] Method 3:

[0027] A solvent is optionally added to bromethrin and additives to form a grinding material, which is then co-ground to obtain a new crystal form of bromethrin; preferably, the material is co-ground in a ball mill to obtain the new crystal form of bromethrin.

[0028] As a preferred implementation method, in methods one, two, and three,

[0029] The additive is selected from at least one of custom additives, template additives, or compound additives; and / or,

[0030] Based on the total weight of bromocyanamide and additives being 100%, the amount of additives added is 0.01% to 20% of the total weight of the feed, preferably 0.5% to 5%.

[0031] Preferably,

[0032] Customized additives (customized additives are the most studied type of additive. These additives are often one or a class of molecules with a similar molecular structure to the solute, and they significantly influence the physicochemical properties of the main molecules in the solution, including their crystal habit, melting point, nucleation, and crystallization behavior) are selected from at least one of neonicotinoids, oxadiazines, or diamides; and / or,

[0033] The template additive (also called a heterogeneous nucleating agent, which generally has specific interactions with the host molecule, such as strong interactions between functional groups, thereby enabling crystal nucleation and growth on its surface to obtain a product with a specific crystal form. Several different materials have been used to study the mechanism of action of this additive on polymorphic nucleation) is selected from at least one of cellulose compounds or synthetic polymer compounds; and / or,

[0034] The composite additive (composite additives, which usually refer to some complex salts, such as polycarbonates, phosphates, ammonium salts, etc., in the solution system, these additives have both electrostatic interactions with certain crystal faces of the crystal and strong interactions with the groups exposed on the crystal surface, thereby achieving the effect of selective adsorption of additive molecules on the crystal face) is selected from at least one of imidazole salts, quaternary ammonium salts, pyridine salts, lignin sulfonates, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide, metformin hydrochloride or N-butylpyridine tetrafluoroborate;

[0035] More preferably,

[0036] Neonicotinoids are selected from at least one of imidacloprid, flonicamid, dinotefuran, chlorpyrifos, acetamiprid, thiamethoxam, thiamethoxam, epoxiconazole, thiamethoxam, piperazine, flupyrflufenone, flonicamid, or acetamiprid; and / or,

[0037] Oxadiazine compounds are selected from indoxacarb; and / or,

[0038] The diamide compound is selected from at least one of cyclobrombutamide, flubendiamide, tetrazolium acetamiprid, tetrachlorantraniliprole, chlorantraniliprole, flubendiamide, chlorfluazuron, cyclopropamide, thiofenoxam, brofenoxam, thiamethoxam, thiofenoxam, fluoxastrobin, fluoxastrobin, isoxastrobin, or cyclopropamide; and / or,

[0039] Cellulose compounds are selected from at least one of hydroxypropyl methylcellulose, cellulose acetate, hydroxyethyl cellulose, or methylcellulose; and / or,

[0040] The synthetic polymer compounds are selected from at least one of polyacrylamide, polyacrylic acid, polyvinyl alcohol, or polyvinylpyrrolidone; and / or,

[0041] The imidazole salt is selected from at least one of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium acetate, or 1-butyl-3-methylthiocyanate imidazole; and / or,

[0042] The quaternary ammonium salt is selected from at least one of tetrabutylphosphine chloride and tetrabutylammonium bisulfate.

[0043] As a preferred implementation method, in method one and method three,

[0044] The solvent is selected from at least one of water, water-soluble organic solvents, or water-insoluble organic solvents; preferably, the water-soluble organic solvent is selected from at least one of ketones, alcohols, or nitriles; and / or, the water-insoluble organic solvent is selected from at least one of hydrocarbons or haloalkanes; more preferably, the ketone solvent is selected from at least one of methyl ethyl ketone, acetophenone, acetone, or butanone; and / or, the alcohol solvent is selected from at least one of methanol, ethanol, isopropanol, or n-butanol; and / or, the nitrile solvent is selected from at least one of acetonitrile or butanone; and / or, the hydrocarbon is selected from at least one of n-heptane, n-octane, nonane, cyclohexane, methylcyclohexane, petroleum ether, naphtha, ethylbenzene, mesitylene, toluene, or xylene; and / or, the haloalkanes are selected from at least one of dichloromethane, trichloromethane, tetrachloromethane, trifluorotoluene, chlorobenzene, dichlorobenzene, or trichlorobenzene; and / or,

[0045] In method two,

[0046] The high-boiling-point compound is selected from at least one of the following: a polymeric compound with a boiling point ≥80℃ or a high-boiling-point solvent with a boiling point ≥80℃;

[0047] Preferably, the polymer compound is selected from polymer compounds with a melting point ≤240℃ and a boiling point ≥80℃; more preferably, the polymer compound is selected from polymer compounds with a melting point ≤100℃ and a boiling point ≥80℃, and which can maintain a liquid state at ≤100℃; even more preferably, the polymer compound is selected from at least one of polyacrylic acid, polyvinylpyrrolidone, polymaleic anhydride, polyquaternary ammonium salt, or polyethylene glycol; and / or, even more preferably, the polyquaternary ammonium salt is selected from polyquaternium-11.

[0048] The high-boiling-point solvent is selected from at least one of fatty acid esters, aromatic esters, phosphate esters, amides, organofluorine compounds, alcohols, 2,4-di-tert-amylphenol, 2,2-dimethyl-6-dodecyloxybenzotetrahydropyran, octanol, or 2-pyrrolidone; more preferably...

[0049] Fatty acid esters and aromatic esters are selected from at least one of dibutyl phthalate, dicyclohexyl phthalate, isooctyl benzoate, sorbitol laurate, isooctadecyl 2-hydroxypropionate, isononyl 4,5-epoxy phthalate, trioctyl citrate, or monobenzoyl 2-octadecyl succinate; and / or,

[0050] Phosphate compounds are selected from at least one of tricresyl phosphate, tricyclohexyl phosphate, dioctyl butyl phosphate, diethylphenyl phosphate, diphenoxyethyl ethyl phosphate, or tri-p-isopropylphenyl phosphate; and / or,

[0051] The amide compound is selected from at least one of lauroyl diethylamine, lauroyl dibutylamine, hexadecyl dimethylamine, thionyl bis(diethylamine), butyrolactone 4'-diethylaminoisoamylamine, or valerate octylamine; and / or,

[0052] The organofluorine compound is selected from at least one of octafluoropentyl laurate, dodecyl fluoroheptyl hexanoate, dodecyl fluoroheptyl laurate, octafluoropentyl diethylamine, difluoropentyl methylphenylamine, or p-butylbenzoate octafluoropentyl laurate; and / or,

[0053] The alcohol compound is selected from at least one of cyclohexanol or glycerol.

[0054] In the technical solution of this invention, polyquaternary ammonium salt-11 is also known as poly[dimethylaminoethyl sulfate diethyl 2-methacrylate-CO(1-vinyl-2-pyrrolidone)].

[0055] As a preferred implementation method, in method one,

[0056] In Method 1,

[0057] Add 3-40 times the volume of solvent to bromocyanamide and mix to obtain a mixture; preferably, add 3-20 times the volume of solvent and mix; more preferably, mix at a temperature between room temperature and the boiling point of the solvent; even more preferably, mix under stirring; and / or,

[0058] If the mixture is a homogeneous solution, the crystallization treatment method shall be selected from at least one of the following methods:

[0059] a: The homogeneous solution is evaporated or subjected to vacuum distillation to reduce the solvent volume and obtain a concentrated solution, thereby reducing the supersaturation of the homogeneous solution and allowing the compound to crystallize in the solution; preferably, the volume of the concentrated solution is 1-10 times, more preferably 1-5 times, the volume of cyantraniliprole; or...

[0060] b: The homogenized solution is cooled once and then added to the additive, optionally followed by a second cooling to crystallize; preferably, the temperature of the first cooling is room temperature - 60°C, more preferably 25-35°C; the temperature of the second cooling is 0°C - room temperature; more preferably 0-10°C; or...

[0061] c: Add an antisolvent to the homogeneous solution, optionally cool it down, and then crystallize it; wherein the antisolvent is an antisolvent miscible with the solvent in step (1); preferably, the amount of the antisolvent added is 0.5-20 times the volume of the solvent added in step (1), more preferably 3-10 times the volume of the solvent added in step (1); and / or, the antisolvent is selected from at least one of water, n-heptane, cyclohexane, or petroleum ether; and / or, the cooling temperature is 0°C to room temperature; and / or,

[0062] If the mixture is a suspension, the crystallization treatment method is as follows:

[0063] After adding the additive to the suspension, the mixture is stirred to carry out crystallization transformation; the preferred stirring time is 1-72 h; the stirring temperature is 25-50 °C.

[0064] In Method 1, the solvent used for washing is the same as the solvent used in step (1) to prepare the homogeneous solution.

[0065] As a preferred implementation method, in method two,

[0066] The volume ratio of bromocyanamide to the high-boiling-point compound is 1:0.5-20; preferably 1:1-10; and / or,

[0067] The melt is placed at 40-130°C for complete crystallization; preferably, the melt is placed at 60-100°C for complete crystallization, and then cooled to obtain a new crystal form of bromocyanamide.

[0068] As a preferred implementation method, in method three,

[0069] The volume of solvent added to broflanilide and the additive is 0-0.5 times the sum of the volumes of broflanilide and the additive; preferably 0.3-0.4; and / or,

[0070] The grinding conditions are 15-30Hz, preferably 20-30Hz; and / or,

[0071] The grinding time is 1-300 minutes; preferably, the grinding time is 50-120 minutes.

[0072] A third objective of this invention is to provide a novel crystal form of bromocyanamide, as described in one objective of this invention, for use in pesticides; preferably, for use in insecticides; and more preferably, for use in insecticides for controlling pests of the Lepidoptera, Hemiptera, Coleoptera, Thysanoptera, Hymenoptera, Amitaria, and Diptera orders.

[0073] In the technical solution of this invention, the pests belonging to the orders Lepidoptera, Hemiptera, Coleoptera, Thysanoptera, Hymenoptera, Acarida, and Diptera are selected from the following groups: diamondback moth, fall armyworm, tobacco shoot armyworm, beet armyworm, white spot armyworm, peach aphid, cotton aphid, potato leafhopper, silver leaf fly, American serpentine leafminer, thrips, beet armyworm, cabbage caterpillar, aphid, yellow-striped flea beetle, cotton bollworm, tobacco whitefly, rice stem borer, rice leaf roller, corn borer, whitefly, spider mite, spider spider, black carpenter ant, kitchen ant, corn ant, bean pod borer, leaf miner, etc., at least one or a combination thereof. The novel crystalline form of cyantraniliprole of this invention has insecticidal effects on all the aforementioned pests. Cyantraniliprole mainly works by activating ryanodine receptors in the target pests. Once activated, these receptors release calcium ions stored in striated and smooth muscle cells, causing muscle movement regulation disorder and paralysis in the pests within minutes, leading to rapid cessation of feeding and eventual death. Therefore, cyantraniliprole has a broad insecticidal spectrum, controlling both chewing and piercing-sucking pests.

[0074] A fourth objective of this invention is to provide a pesticide composition comprising a novel crystal form of bromocyanamide as described in one objective of this invention;

[0075] Preferably, the pesticide composition further includes adjuvants;

[0076] More preferably, the additives include at least one of wetting agents, emulsifiers, dispersants, adhesives, stabilizers, synergists, thickeners, and defoamers;

[0077] More preferably, the new crystal form of bromocyanamide in the pesticide composition has a mass content of 1%-99.9%, more preferably 1%-60%.

[0078] 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.

[0079] Compared with the prior art, the present invention has the following advantages:

[0080] This invention discovers a new crystal form of bromocyanamide, which has superior properties and higher biological activity.

[0081] The method for preparing the new crystal form (i.e., crystal form II) of bromocyanamide of the present invention is simple and suitable for large-scale industrial production.

[0082] The crystal form of this invention can be used for the control of pests in the orders Lepidoptera, Hemiptera, Coleoptera, Thysanoptera, Hymenoptera, Amitaria, and Diptera. Crystal form II is more effective than crystal form I in controlling pests in crops such as corn, sugarcane, and cotton. Attached Figure Description

[0083] Figure 1 The powder X-ray diffraction (PXRD) pattern of crystal form I of bromocyanamide in the prior art;

[0084] Figure 2 The powder X-ray diffraction (PXRD) pattern of crystal form II of the bromocyanamide of the present invention is shown.

[0085] Figure 3 The differential scanning calorimetry (DSC) spectrum of crystal form I of bromocyanamide in the prior art is shown.

[0086] Figure 4 The differential scanning calorimetry (DSC) spectrum of crystal form II of the bromocyanamide of the present invention is shown.

[0087] Figure 5 This is an oak ridge thermal ellipsoid diagram of crystal form II of the bromoxynil of the present invention;

[0088] Figure 6 This is a cell structure diagram of crystal form II of the bromocyanamide of the present invention;

[0089] Figure 7 Powder X-ray diffraction (PXRD) pattern of crystal form II of bromocyanamide prepared according to another embodiment of the present invention;

[0090] Figure 8 Powder X-ray diffraction (PXRD) pattern of crystal form II of bromocyanamide prepared according to another embodiment of the present invention. Detailed Implementation

[0091] 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.

[0092] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0093] Test method:

[0094] 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 from 3 to 40° in the 2θ interval, and the scanning speed was 10° / min.

[0095] Measurement discrepancies associated with these powder X-ray diffraction (PXRD) 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 PXRD peak positions. Systematic studies have shown that a 1 mm difference in sample height can result in peak shifts as high as 1° at 2θ. These shifts can be identified from the powder 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.

[0096] DSC (Differential Scanning Calorimetry) method: Instrument model: DSC8231, using N2 atmosphere, heating rate is 5℃ / min.

[0097] Comparative Example 1

[0098] Preparation of crystal form I:

[0099] Weigh approximately 5g of cyantraniliprole into a 1L Erlenmeyer flask, add 30mL of DMF and stir at room temperature (200rpm) until dissolved. Slowly add methanol / water (volume ratio 2:1) at a rate of 2-3 drops / s, for a total of approximately 400mL. After adding about 200mL, solid begins to precipitate. After the addition is complete, a significant amount of solid precipitates. Allow the crystals to crystallize at room temperature for 3-4 hours. Filter the solution and wash the solid with an appropriate amount of methanol / water (2:1). After filtration, small white granular solid particles are obtained. Dry the particles in a vacuum drying oven at 50℃ for 24 hours. The resulting powder is crystal form I.

[0100] The bromocyanamide used in the following embodiments of the present invention is the bromocyanamide powder prepared in Comparative Example 1, that is, using crystal form I as raw material.

[0101] Example 1

[0102] Preparation of crystal form II:

[0103] Take 1g of bromocyanamide and 10% of additive (tetrachlorantraniliprole), add 0.1 times the volume of solvent (n-butanol), and grind them together in a ball mill at 20Hz for 20 minutes. Place the powder in a vacuum dryer at 80℃ for 12 hours to obtain bromocyanantraniliprole crystal form II.

[0104] In Example 1 of this invention, 10% additive means that the amount of additive added is 10% of the total weight of the feed, calculated based on 100% of the total weight of bromocyanamide and additive. Similar expressions in the following examples using a preparation method similar to that of Example 1 can be understood according to the measurement method described above in Example 1.

[0105] In Example 1 of this invention, adding 0.1 times the volume of solvent means that the volume of solvent added is 0.1 times the sum of the volumes of bromocyanamide and the additive. Similar expressions in the following examples using a preparation method similar to that of Example 1 can be understood according to the measurement method described above in Example 1.

[0106] Example 2

[0107] Preparation of crystal form II:

[0108] Take 1g of bromocyanamide and 8% additive (imidacloprid), add 0.1 times the volume of isopropanol, and grind them together in a ball mill at 30Hz for 30 minutes. Place the powder in a vacuum dryer at 80℃ for 12 hours to obtain bromocyanamide crystal form II.

[0109] Example 3

[0110] Preparation of crystal form II:

[0111] Take 1g of bromocyanamide and 8% additive (indoxacarb, molten state), grind them together in a ball mill at 30Hz for 60 minutes, and dry the powder under vacuum at 80℃ for 12 hours to obtain bromocyanamide crystal form II.

[0112] Example 4

[0113] Preparation of crystal form II:

[0114] Take 1g of bromocyanamide and 5% of additive (tetrachlorantraniliprole, molten state), add 0.2 times the amount of acetonitrile solvent, and grind them together in a ball mill at 30Hz for 60 minutes. Place the powder in a vacuum dryer at 80℃ for 12 hours to obtain bromocyanantraniliprole crystal form II.

[0115] Example 5

[0116] Preparation of crystal form II:

[0117] 1 g of bromocyanamide was placed in a single-necked round-bottom flask, and 20 mL of isopropanol was added. The mixture was stirred at 25 °C to obtain a suspension. 20 mg of piperazine was added, and the solution was then suspended at 25 °C and 500 rpm for 48 h to allow complete conversion. The solution was then filtered, washed with a small amount of isopropanol, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0118] Example 6

[0119] Preparation of crystal form II:

[0120] 1 g of bromocyanamide was placed in a single-necked round-bottom flask, and 20 mL of water was added. The mixture was stirred at 25 °C to obtain a suspension. 20 mg of cellulose acetate was added, and the solution was then suspended at 25 °C and 500 rpm for 48 h to allow complete conversion. The solution was then filtered, washed with a small amount of water, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0121] Example 7

[0122] Preparation of crystal form II:

[0123] 1 g of bromocyanamide was placed in a single-necked round-bottom flask, and 50 mL of isopropanol was added. The mixture was stirred at 25 °C to obtain a homogeneous solution. The insoluble matter was filtered off, and 20 mg of flubendiamide was added. The solution was then concentrated under reduced pressure at 25 °C to 4 mL. As the solution concentrated, transparent, colorless crystals precipitated in the flask. The crystals were then filtered, washed with a small amount of isopropanol, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0124] Example 8

[0125] Preparation of crystal form II:

[0126] 1 g of bromocyanamide was placed in a single-necked round-bottom flask, and 65 mL of n-propanol was added. The mixture was stirred at 60 °C to obtain a homogeneous solution. The insoluble matter was filtered off, and 20 mg of hydroxypropyl methylcellulose was added. The solution was then cooled to 25 °C and allowed to evaporate slowly. As the solvent evaporated, transparent, colorless crystals precipitated in the flask. The crystals were then filtered, washed with a small amount of n-propanol, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0127] Example 9

[0128] Preparation of crystal form II:

[0129] 1 g of bromocyanamide was placed in a single-necked round-bottom flask, and 55 mL of n-butanol was added. The mixture was stirred at 25 °C to obtain a homogeneous solution. The insoluble matter was filtered off, and the solution was then cooled to 0 °C. 0.01 g of hydroxyethyl cellulose was added, and transparent colorless crystals precipitated in the flask. The crystals were then filtered, washed with a small amount of n-butanol, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0130] Example 10

[0131] Preparation of crystal form II:

[0132] 10 g of cyantraniliprole was placed in a three-necked round-bottom flask, and 50 mL of methanol was added. The slurry was stirred and heated to its boiling point to dissolve it and obtain a homogeneous solution. The insoluble matter was filtered off, and the mixture was stirred and cooled to 0 °C. 0.001 g of polyacrylamide was added as a seed crystal, and a white solid powder precipitated. The resulting slurry was stirred at 0 °C for 2 h. The slurry was then filtered, and the obtained solid was washed with 2 mL of methanol pre-cooled to 0 °C. The obtained solid was dried under vacuum at 80 °C for 12 h to obtain cyantraniliprole crystal form II.

[0133] Example 11

[0134] Preparation of crystal form II:

[0135] 10 g of cyantraniliprole was placed in a three-necked round-bottom flask, and 30 mL of methanol was added. The slurry was stirred and heated to dissolve it and obtain a homogeneous solution. The insoluble matter was filtered off, and then the solution was slowly cooled to 25 °C. 0.005 g of dibutyl phthalate was added as a seed crystal. The mixture was stirred and cooled to 0 °C. A white solid powder precipitated out. The resulting slurry was stirred at 0 °C for 2 h. The slurry was then filtered, and the solid was washed with 2 mL of methanol pre-cooled to 0 °C. The solid was dried under vacuum at 80 °C for 12 h to obtain cyantraniliprole crystal form II.

[0136] Example 12

[0137] Preparation of crystal form II:

[0138] 10 g of cyantraniliprole was placed in a three-necked round-bottom flask, and 40 mL of ethanol was added. The slurry was stirred and heated to dissolve it and obtain a homogeneous solution. The insoluble matter was filtered off, and then the solution was slowly cooled to 35 °C. 0.5 g of metformin hydrochloride was added as a seed crystal. The mixture was stirred and cooled to 0 °C. A white solid powder precipitated out. The resulting slurry was stirred at 0 °C for 2 h. The slurry was then filtered, and the solid was washed with 2 mL of ethanol pre-cooled to 0 °C. The solid was dried under vacuum at 80 °C for 12 h to obtain cyantraniliprole crystal form II.

[0139] Example 13

[0140] Preparation of crystal form II:

[0141] 10g of cyantraniliprole was placed in a three-necked round-bottom flask, and 20mL of acetone was added. The mixture was stirred at 25°C to obtain a homogeneous solution. The insoluble matter was filtered off, and 2g of cyantraniliprole crystal form II was added as a seed crystal. Then, 100mL of water was slowly added. A white solid powder precipitated out. The resulting slurry was cooled to 0°C and stirred for 2 hours. The slurry was then filtered, and the resulting solid was washed with 5mL of acetone pre-cooled to 0°C. The resulting solid was dried under vacuum at 80°C for 12 hours to obtain cyantraniliprole crystal form II.

[0142] Example 14

[0143] Preparation of crystal form II:

[0144] 2 g of cyantraniliprole was placed in a single-necked round-bottom flask, and 45 mL of methyl ethyl ketone was added. The mixture was stirred at room temperature to obtain a homogeneous solution. The insoluble matter was filtered off, and the solution was slowly evaporated at 10 °C. As the solvent evaporated, transparent colorless crystals precipitated in the flask. The solution was then filtered, washed with a small amount of methyl ethyl ketone, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain cyantraniliprole crystal form II.

[0145] Example 15

[0146] Preparation of crystal form II:

[0147] 10 g of bromocyanamide was placed in a three-necked round-bottom flask, and 50 mL of dichloromethane was added. The slurry was stirred and heated to its boiling point to dissolve it and obtain a homogeneous solution. The insoluble matter was filtered off, and the mixture was stirred and cooled to 0 °C. 0.001 g of polyvinyl alcohol was added as a seed crystal, and the solution was allowed to evaporate slowly at 0 °C. As the solvent evaporated, transparent colorless crystals precipitated in the flask. The slurry was then filtered, and the resulting solid was washed with 2 mL of dichloromethane pre-cooled to 0 °C. The resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0148] Example 16

[0149] Preparation of crystal form II:

[0150] 1 g of bromocyanamide was placed in a single-necked round-bottom flask, and 30 mL of methanol was added. The mixture was stirred at 25 °C to obtain a homogeneous solution. The insoluble matter was filtered off, and 20 mg of cyclophosphamide was added. Then, 30 mL of a low-solubility aqueous solvent was added to the homogeneous solution. With the addition of the impure solution, transparent, colorless crystals precipitated in the flask. The solution was then filtered, washed with a small amount of methanol, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0151] Example 17

[0152] Preparation of crystal form II:

[0153] 1 g of cyantraniliprole was placed in a single-necked round-bottom flask, and 20 mL of acetone was added. The mixture was stirred at 25 °C to obtain a homogeneous solution. The insoluble matter was filtered off, and 20 mg of flonicamid was added. Then, 30 mL of heptane, a solvent with low solubility, was added to the homogeneous solution. With the addition of the undesirable solvent, transparent, colorless crystals precipitated in the flask. The crystals were then filtered, washed with a small amount of acetone, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain cyantraniliprole crystal form II.

[0154] Example 18

[0155] Preparation of crystal form II:

[0156] 1 g of bromocyanamide was placed in a single-necked round-bottom flask, and 60 mL of acetonitrile was added. The mixture was stirred at 25 °C to obtain a homogeneous solution. The insoluble matter was filtered off, and 20 mg of thiamethoxam was added. Then, 30 mL of petroleum ether solvent with low solubility was added to the homogeneous solution. With the addition of the solution, transparent, colorless crystals precipitated in the flask. The crystals were then filtered, washed with a small amount of acetonitrile, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0157] Example 19

[0158] Preparation of crystal form II:

[0159] 1 g of cyantraniliprole was placed in a single-necked round-bottom flask, and 50 mL of dichloromethane was added. The mixture was stirred at 25 °C to obtain a homogeneous solution. The insoluble matter was filtered off, and 20 mg of tetrachlorantraniliprole was added. Then, 30 mL of cyclohexane, a solvent with low solubility, was added to the homogeneous solution. With the addition of this solution, transparent, colorless crystals precipitated in the flask. The crystals were then filtered, washed with a small amount of dichloromethane, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain cyantraniliprole crystal form II.

[0160] Example 20

[0161] Preparation of crystal form II:

[0162] 1 g of bromocyanamide was placed in a single-necked round-bottom flask, and 40 mL of ethanol was added. The mixture was stirred at 25 °C to obtain a homogeneous solution. The insoluble matter was filtered off, and 20 mg of fluoxetine was added. Then, 20 mL of petroleum ether solvent with low solubility was added to the homogeneous solution. With the addition of the solution, transparent, colorless crystals precipitated in the flask. The crystals were then filtered, washed with a small amount of ethanol, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0163] Example 21

[0164] Preparation of crystal form II:

[0165] 1 g of bromocyanamide was placed in a single-necked round-bottom flask, and 45 mL of methyl ethyl ketone was added. The mixture was stirred at 25 °C to obtain a homogeneous solution. The insoluble matter was filtered off, and 20 mg of thiamethoxam was added. Then, 20 mL of heptane, a solvent with low solubility, was added to the homogeneous solution. With the addition of the solution, transparent, colorless crystals precipitated in the flask. The crystals were then filtered, washed with a small amount of ethanol, and the resulting solid was dried under vacuum at 80 °C for 12 h to obtain bromocyanamide crystal form II.

[0166] Example 22

[0167] Preparation of crystal form II:

[0168] Take 1g of bromocyanamide and 2mL of dibutyl phthalate and heat them together to 160℃ until they are completely melted to obtain a homogeneous melt. Add 2mg of flubendiamide to the melt, and then lower the temperature to 60℃ to allow it to cool and grow. After the growth is complete, filter and wash with a small amount of water. Dry the obtained solid under vacuum at 80℃ for 12h to obtain bromocyanamide crystal form II.

[0169] Example 23

[0170] Preparation of crystal form II:

[0171] Take 1g of bromocyanamide and 3mL of tricresyl phosphate and heat them together to 150℃ until they are completely melted to obtain a homogeneous melt. Add 5mg of cellulose acetate to the melt, and then lower the temperature to 50℃ to allow it to cool and grow. After growth is complete, filter and wash with a small amount of water. Dry the obtained solid under vacuum at 80℃ for 12h to obtain bromocyanamide crystal form II.

[0172] Example 24

[0173] Preparation of crystal form II:

[0174] Take 1g of chlorantraniliprole and 5mL of polyvinylpyrrolidone and heat them together to 150℃ until they are completely melted to obtain a homogeneous melt. Add 10mg of chlorantraniliprole to the melt, and then lower the temperature to 100℃ to allow it to cool and grow. After the growth is complete, collect the solid, wash it with a small amount of water, and dry the obtained solid under vacuum at 80℃ for 12h to obtain chlorantraniliprole crystal form II.

[0175] Example 25

[0176] Preparation of crystal form II:

[0177] Take 1g of cyantraniliprole and 6mL of hexadecyl dimethylamine and heat them together to 150℃ until they are completely melted to obtain a homogeneous melt. Add 10mg of tetrachlorantraniliprole to the melt, and then lower the temperature to 60℃ to allow it to cool and grow. After the growth is complete, collect the solid, wash it with a small amount of water, and dry the obtained solid under vacuum at 80℃ for 12h to obtain cyantraniliprole crystal form II.

[0178] Example 26

[0179] Preparation of crystal form II:

[0180] Take 1g of bromocyanamide and 8mL of polyquaternium-11 and heat them together to 150℃ until they are completely melted to obtain a homogeneous melt. Add 10mg of sodium lignosulfonate to the melt, and then lower the temperature to 80℃ to allow it to cool and grow. After the growth is complete, collect the solid, wash it with a small amount of water, and dry the obtained solid under vacuum at 80℃ for 12h to obtain bromocyanamide crystal form II.

[0181] All of the above embodiments of the present invention can obtain crystal form II. For the sake of patent brevity, the present invention lists the test results of several embodiments, as follows:

[0182] The PXRD pattern of crystal form II obtained in Example 7 is shown in [reference needed]. Figure 2 ;

[0183] The PXRD pattern of crystal form II obtained in Example 1 is shown below. Figure 7 ;

[0184] The PXRD pattern of crystal form II obtained in Example 23 is shown below. Figure 8 ,

[0185] in, Figure 2 The specific diffraction angle data corresponding to the PXRD pattern of crystal form II obtained in Example 7 are shown in Table 1 below.

[0186] Table 1. PXRD data for crystal form II

[0187]

[0188]

[0189] The crystal form II obtained in Examples 1 and 23 has the same 2θ±0.2° diffraction angle as the crystal form II obtained in Example 7. The only difference is the intensity of the diffraction angle. The PXRD data of the crystal form II obtained in Examples 1 and 23 will not be listed here.

[0190] The DSC spectrum of crystal form II prepared in Example 7 is basically as follows: Figure 4 As shown, the first endothermic peak corresponds to the melting process of crystal form II at 205-215℃, with a peak temperature of around 212.7℃. No crystal transformation peak was found, indicating that the prepared crystal form II is thermodynamically stable.

[0191] In addition, the single-crystal X-ray diffraction (SCXRD) structure of crystal form II in Example 7 was also obtained (e.g. Figure 5 , Figure 6 As shown in Table 2, its parameters are as follows:

[0192] Table 2. X-ray diffraction parameters of single crystal of crystal form II

[0193]

[0194]

[0195] Example 27

[0196] Physical stability experiment 1:

[0197] 200 mg each of crystal form I powder and crystal form II powder obtained in Example 7 were placed in 20 mL of deionized water and 20 mL of methyl oleate, respectively, and suspended at 25°C and 200 rpm with stirring. Samples were taken at 3h, 6h, 12h, 24h, and 48h, 4 mL each time. The dispersion medium was removed by filtration, and the samples were dried in a vacuum drying oven before PXRD testing. Crystal forms I and II were stable in water and methyl oleate, and no phase transition was observed. These results indicate that the stability of crystal form II is comparable to that of crystal form I, and it has good stability in both water and oil media. For subsequent property evaluation, it is essential to ensure that the solid form of bromocyanamide maintains its original crystal form in the formulation. Therefore, water is the best choice as the dispersion medium. Suspension concentrate (SC) is an ideal formulation of bromocyanamide, while oil suspension concentrate (OD) is more suitable for the development of multiple formulations.

[0198] Example 28

[0199] Physical stability experiment 2:

[0200] 50 mg each of crystal form I powder and crystal form II obtained in Example 7 were prepared into a 500 mg / L suspension according to Example 27. The suspensions were stored in a 54°C oven for 14 days. Samples (6 mL each) were taken on days 3, 7, and 14. After centrifugation, the supernatant was discarded, and the suspensions were washed with water until no obvious impurities were observed. After thorough drying, PXRD testing was performed. Crystal forms I and II were stable in the prepared suspension, with no phase transition occurring. This experiment demonstrates that crystal form II can exist stably in this suspension system, and this suspension formulation can be used for subsequent property testing.

[0201] Example 29

[0202] Indoor bioactivity assay of insecticides:

[0203] 1. Experimental Samples:

[0204] The cyantraniliprole crystal form I prepared in Comparative Example 1 and the cyantraniliprole crystal form II prepared in Example 7 above.

[0205] 2. Compound preparation:

[0206] Weigh a certain mass of the above experimental samples using an analytical balance (0.00001g) and dissolve them in a 500mg / L stock solution with 0.1wt% Tween-80 emulsifier.

[0207] 3. Experimental methods:

[0208] Leaf dipping method: Dilute the stock solution to 5 mg / L with distilled water, then dilute to the test concentration with distilled water containing 0.1 wt% Tween-80. The test targets are fall armyworm or corn borer larvae. After thoroughly soaking an appropriate amount of corn leaves in the prepared solution, place them in a petri dish lined with filter paper and allow them to air dry naturally. Inoculate each dish with 10 mid-3rd instar fall armyworm or corn borer larvae and incubate in a 24-27℃ observation room. Investigate the results after 48 hours. Touch the insect with a paintbrush; severe poisoning is considered fatal. The test concentrations were 5, 2.5, 1.5, 0.8, 0.4, 0.2, and 0.1 mg / L.

[0209] 4. Experimental Results:

[0210] The results of the insecticidal activity tests of crystal form I and crystal form II are shown in Table 3. The results showed that after leaf dipping treatment, at 5 mg / L, the mortality rates of the test insects (fall armyworm) treated with crystal form I and crystal form II were 86.67% and 100%, respectively, and the mortality rates of the test insects (corn borer) were 63.33% and 90%, respectively. It is also worth mentioning that the insecticidal activity of crystal form II against fall armyworm was 6.37 times that of crystal form I, and against corn borer it was 3.59 times that of crystal form I.

[0211] Table 3. Comparison of insecticidal activity between crystal form I and crystal form II.

[0212]

[0213] Crystal form I 5 86.67 Crystal form I 5 63.33 2.5 71 2.5 50 1.5 50 1.5 40 0.8 36.67 0.8 33.33 0.4 16.67 0.4 20 0.2 6.7 0.2 10 0.1 0 0.1 0 Crystal form II 5 100 Crystal form II 5 90 2.5 100 2.5 76.67 1.5 100 1.5 63.33 0.8 90 0.8 53.33 0.4 73.33 0.4 40 0.2 43.33 0.2 26.67 0.1 23.33 0.1 16.67

[0214] As can be seen from the table above, the advantage of this invention lies in the fact that, at the same concentration, the insecticidal effect of crystal form II is better than that of crystal form I.

[0215] 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.

[0216] 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.

[0217] 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.

[0218] 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 novel crystalline form of bromocyanamide, characterized in that: The crystal form includes a powder X-ray diffraction pattern with characteristic peaks at 8.70, 9.94, 11.24, 12.24, 22.38, and 24.70, expressed as a diffraction angle of 2θ ± 0.2°.

2. The new crystalline form of bromocyanamide according to claim 1, characterized in that: The crystal form also has one or more additional peaks at 20.20, 20.74, 22.14, 23.54, 24.70, and 25.18 in the powder X-ray diffraction pattern expressed as 2θ±0.2° diffraction angle.

3. The new crystalline form of bromocyanamide according to claim 2, characterized in that: The crystal form also has one or more additional peaks at 10.72, 11.82, 16.02, 21.38, 22.68, 26.06, and 29.50 in the powder X-ray diffraction pattern expressed as 2θ±0.2° diffraction angle.

4. The new crystalline form of bromocyanamide according to claim 3, characterized in that: The crystal form also has one or more additional peaks in its powder X-ray diffraction pattern, expressed as a diffraction angle of 2θ ± 0.2°, at 13.78, 14.16, 14.62, 16.56, 17.44, 24.32, 27.00, 27.24, 27.66, 28.08, 28.64, 28.92, 30.22, 30.60, 30.94, 31.82, 32.56, 33.10, 34.10, 34.62, 35.38, 36.14, 36.54, 37.16, 38.24, and 38.

94.

5. The novel crystalline form of bromocyanamide according to claim 4, characterized in that: The powder X-ray diffraction pattern of the crystal form is shown in Figure 2.

6. A method for preparing a novel crystalline form of bromocyanamide as described in any one of claims 1-5, characterized in that, Includes one of the following methods: Method 1: (1) Mix bromocyanamide with a solvent to obtain a mixture; (2) Add additives to the mixture, then crystallize, separate solids and liquids, wash, and obtain a new crystal form of bromocyanamide; based on the total weight of bromocyanamide and additives being 100%, the amount of additives added is 0.01%~20% of the total weight of the feed. or, Method 2: (1) After heating bromocyanamide and a high-boiling-point compound together until completely melted, a melt is obtained; the boiling point of the high-boiling-point compound is ≥80℃; (2) Add additives to the melt, and then crystallize the melt to obtain a new crystal form of bromocyanamide; based on the total weight of bromocyanamide and additives being 100%, the amount of additives added is 0.01% to 5% of the total weight of the additives; or, Method 3: Solvents are optionally added to bromethrin and additives to form a grinding paste, which is then co-ground to obtain a new crystal form of bromethrin; the amount of additives added is 0.01% to 10% of the total weight of bromethrin and additives, which is 100% of the total weight of the feed. In method two, The volume ratio of bromocyanamide to the high-boiling-point compound is 1:0.5-20; the high-boiling-point compound is selected from at least one of a polymeric compound with a boiling point ≥80℃ or a high-boiling-point solvent with a boiling point ≥80℃; the polymeric compound is selected from at least one of polyacrylic acid, polyvinylpyrrolidone, polymaleic anhydride, polyquaternary ammonium salt or polyethylene glycol; The high-boiling-point solvent is selected from at least one of fatty acid esters, aromatic esters, phosphates, amides, organofluorine compounds, alcohols, 2,4-di-tert-amylphenol, 2,2-dimethyl-6-dodecyloxybenzotetrahydropyran, octanol, or 2-pyrrolidone. The fatty acid esters and aromatic esters are selected from at least one of dibutyl phthalate, dicyclohexyl phthalate, isooctyl benzoate, sorbitol laurate, isooctadecyl 2-hydroxypropionate, isononyl 4,5-epoxyphthalate, trioctyl citrate, or monobenzoyl 2-octadecyl succinate; the phosphate esters are selected from at least one of tricresyl phosphate, tricyclohexyl phosphate, dioctyl butyl phosphate, diethylphenyl phosphate, diphenoxyethyl ethyl phosphate, or tri-p-isopropylphenyl phosphate. The amide compound is selected from at least one of lauroyl diethylamine, lauroyl dibutylamine, hexadecyl dimethylamine, thionyl bis(diethylamine), butyrolactone 4'-diethylaminoisoamylamine, or valerate octylamine; The organofluorine compound is selected from at least one of octafluoropentyl laurate, dodecyl heptafluoroheptafluoro laurate, dodecyl heptafluoroheptafluoro laurate, octafluoropentyl diethylamine, difluoropentyl methylphenylamine, or p-butylbenzoate octafluoropentyl laurate. The alcohol compound is selected from at least one of cyclohexanol or glycerol; Method 1, Method 2, and Method 3, The additive is selected from at least one of custom additives, template additives, or compound additives; The custom additive is selected from at least one of neonicotinoids, oxadiazines, or diamides; the neonicotinoids are selected from at least one of imidacloprid, flonicamid, dinotefuran, chlorthiazoline, acetamiprid, thiamethoxam, thiamethoxam, epoxiconazole, thiamethoxam, piperazine, flupyrflurane, flonicamid, or acetamiprid. The oxadiazine compounds were selected from indoxacarb; The diamide compounds are selected from at least one of the following: cyclobrombutamide, flufenoxuron, tetrazolium amide, tetrachlorantraniliprole, chlorantraniliprole, flubendiamide, chlorfluazuron, cyclopropamide, thiofenoxuron, brofenoxuron diamide, thiamethoxam, thiofenoxuron, fluoxastrobin, fluoxastrobin, isoxastrobin, or cyclopropoxyfen. The template additive is selected from at least one of cellulose compounds or synthetic polymer compounds; the cellulose compound is selected from at least one of hydroxypropyl methylcellulose, cellulose acetate, hydroxyethyl cellulose, or methylcellulose; the synthetic polymer compound is selected from at least one of polyacrylamide, polyacrylic acid, polyvinyl alcohol, or polyvinylpyrrolidone. The compound additive is selected from at least one of imidazole salts, quaternary ammonium salts, pyridine salts, lignin sulfonates, sodium dodecylbenzenesulfonate, hexadecyltrimethylammonium bromide, metformin hydrochloride, or N-butylpyridine tetrafluoroborate; the imidazole salt is selected from at least one of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium acetate, or 1-butyl-3-methylthiocyanate imidazole; the quaternary ammonium salt is selected from at least one of tetrabutylphosphine chloride and tetrabutylammonium hydrogen sulfate. In Method 1 and Method 3, the solvent is selected from at least one of water, water-soluble organic solvents, or non-water-soluble organic solvents; the water-soluble organic solvent is selected from at least one of ketones, alcohols, or nitriles; and the non-water-soluble organic solvent is selected from at least one of hydrocarbons or haloalkanes.

7. The method for preparing the new crystal form of bromocyanamide according to claim 6, characterized in that: In Method 1 and Method 3, Based on a total weight of bromocyanamide and additives of 100%, the amount of additives added is 0.01% to 5% of the total weight of the feed.

8. The method for preparing the new crystal form of bromocyanamide according to claim 6, characterized in that: The ketone solvents are selected from at least one of methyl ethyl ketone, acetophenone, acetone, or butanone; and / or, the alcohol solvents are selected from at least one of methanol, ethanol, isopropanol, or n-butanol; and / or, the nitrile solvents are selected from at least one of acetonitrile or butanone; and / or, the hydrocarbons are selected from at least one of n-heptane, n-octane, nonane, cyclohexane, methylcyclohexane, petroleum ether, naphtha, ethylbenzene, mesitylene, toluene, or xylene; and / or, the haloalkanes are selected from at least one of dichloromethane, chloroform, carbon tetrachloride, trifluorotoluene, chlorobenzene, dichlorobenzene, or trichlorobenzene.

9. The method for preparing the new crystal form of bromocyanamide according to claim 6, characterized in that: In Method 1, Add 1-40 times the volume of solvent to bromocyanamide and mix to obtain a mixture; and / or, If the mixture is a homogeneous solution, the crystallization treatment method shall be selected from at least one of the following methods: a: The homogeneous solution is evaporated or subjected to vacuum distillation to reduce the amount of solvent, resulting in a concentrated solution. This reduces the supersaturation of the homogeneous solution, allowing the compound to crystallize in the solution; or... b: After cooling the homogenized solution once, add the additive, and optionally cool it a second time to crystallize; or... c: Add an antisolvent to the homogeneous solution, optionally cool it down, and then crystallize it; wherein the antisolvent is an antisolvent miscible with the solvent in step (1); If the mixture is a suspension, the crystallization treatment method is as follows: after adding the additive to the suspension, stir and mix to carry out crystallization transformation; and / or, In Method 1, the solvent used for washing is the same as the solvent used in step (1) to prepare the homogenized solution.

10. The method for preparing the new crystal form of bromocyanamide according to claim 9, characterized in that: In Method 1, 3-20 times the volume of solvent is added to bromocyanamide and mixed to obtain a mixture; and / or, If the mixture is a homogeneous solution, the crystallization treatment method shall be selected from at least one of the following methods: Method a: The volume of the concentrated solution is 1-10 times the volume of cyantraniliprole; or, Method b: The temperature for the first cooling step is room temperature to 60℃; the temperature for the second cooling step is -20℃ to room temperature; or, Method c: The amount of antisolvent added is 0.5-20 times the volume of the solvent added in step (1); and / or, the antisolvent is selected from at least one of water, n-heptane, cyclohexane or petroleum ether; and / or, the cooling temperature is 0℃-room temperature; If the mixture is a suspension, the crystallization treatment method is as follows: after adding the additive to the suspension, stir and mix to carry out crystallization transformation; the stirring and mixing time is 0.1-72 h; the stirring and mixing temperature is 25-50℃.

11. The method for preparing the new crystal form of bromocyanamide according to claim 10, characterized in that: In Method 1, Add 3-20 times the volume of solvent to bromocyanamide and mix to obtain a mixture; the mixing temperature should be within the range of room temperature to the boiling point of the solvent; and / or, If the mixture is a homogeneous solution, the crystallization treatment method shall be selected from at least one of the following methods: Method a: The volume of the concentrated solution is 1-5 times the volume of cyantraniliprole; or, Method b: The temperature for the first cooling step is 25-35℃; the temperature for the second cooling step is 0-10℃; or, Method c: The amount of antisolvent added is 3-10 times the volume of the solvent added in step (1).

12. The method for preparing the new crystal form of bromocyanamide according to claim 6, characterized in that: In method two, The volume ratio of bromocyanamide to a high-boiling-point compound is 1:1-10; and / or, The melt was placed at 0-130℃ for complete crystallization, and then cooled to obtain a new crystal form of bromocyanamide.

13. The method for preparing the new crystal form of bromocyanamide according to claim 12, characterized in that: In method two, The melt was placed at 60℃-100℃ for complete crystallization, and then cooled to obtain a new crystal form of bromocyanamide.

14. The method for preparing the new crystal form of bromocyanamide according to claim 6, characterized in that: In method three, The volume of solvent added to broflanilide and the additive is 0-0.5 times the sum of the volumes of broflanilide and the additive; and / or, The grinding time is 1-1200 minutes.

15. The method for preparing the new crystal form of bromocyanamide according to claim 14, characterized in that: In method three, The volume of solvent added to broflanilide and the additive is 0.2-0.3 times the sum of the volumes of broflanilide and the additive; and / or, The grinding time is 20-120 minutes.

16. The use of a novel crystalline form of bromocyanamide as described in any one of claims 1-5 in the preparation of pesticides.

17. The application according to claim 16, characterized in that: Application of novel crystalline forms of bromocyanamide in the preparation of insecticide pesticides.

18. The application according to claim 17, characterized in that: Application of the new crystal form of bromocyanamide in the preparation of insecticides for controlling pests of the Lepidoptera, Hemiptera, Coleoptera, Thysanoptera, Hymenoptera, Amitaria, and Diptera orders.

19. A pesticide composition, characterized in that, This includes the novel crystalline form of bromocyanamide as described in any one of claims 1-5.

20. The pesticide composition according to claim 19, characterized in that, The pesticide composition also includes adjuvants.

21. The pesticide composition according to claim 20, characterized in that, The additives include at least one of wetting agents, emulsifiers, dispersants, adhesives, stabilizers, synergists, thickeners, and defoamers.

22. The pesticide composition according to claim 21, characterized in that, In the pesticide composition, the mass content of the new crystal form of bromocyanamide is 1%-99.9%.

23. The pesticide composition according to claim 22, characterized in that, In the pesticide composition, the mass content of the new crystal form of bromocyanamide is 1%-60%.

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