Spirotetramat crystal form II, preparation method thereof, pesticide composition and application thereof

Abstract

The invention relates to the field of pesticides, and discloses a spirotetramat crystal form II, a preparation method of the spirotetramat crystal form II, a pesticide composition and application of the pesticide composition. X-ray powder diffraction of the spirotetramat crystal form II obtained by Cu-K alpha radiation measurement has characteristic peaks at the following diffraction angles expressed by a 2 theta angle: 2 theta = 5.91 + / -0.2 degrees, 2 theta = 7.72 + / -0.2 degrees, 2 theta = 11.0 + / -0.2 degrees, 2 theta = 22.00 + / -0.2 degrees, 2 theta = 22.75 + / -0.2 degrees and 2 theta = 23.37 + / -0.2 degrees. Compared with a spirotetramat amorphous form, the spirotetramat crystal form II has excellent normal-temperature and normal-humidity stability, acceleration stability and mechanical stability, is easy to store and lower in hygroscopicity in a 95% RH high-humidity environment, the preparation method is short in time consumption and high in yield, the time consumed by filtering, washing and drying can be saved, no solvent is used in the preparation process, and the preparation method is suitable for industrial production. The environment is protected.

Description

Technical Field

[0001] The present invention relates to the field of pesticides, and in particular to a spirotetramat crystal form II, a preparation method of spirotetramat crystal form II, a pesticide composition and applications thereof. Background Art

[0002] 4-(Ethoxycarbonyloxy)-8-methoxy-3-(2,5-xylyl)-1-azaspiro[4,5]-dec-3-en-2-one (spirotetramat) is a tetronic acid derivative insecticide that can be used in most crops including but not limited to cotton, soybeans, tropical fruit trees, nuts, grapes, vegetables, etc. to effectively control various piercing-sucking mouthparts pests. It has a bidirectional systemic conduction performance in the xylem and phloem, and can move upward or downward throughout the plant body, thereby controlling pests in hidden parts of the plant body and protecting new stems, leaves, roots and other parts that have not been sprayed. Its mechanism of action is to inhibit the activity of acetyl-CoA carboxylase (ACCase) in the process of fat synthesis in the pest body, inhibit fat synthesis, block the normal metabolic ability of the pest, and cause its death. Spirotetramat mainly acts as a stomach poison, and also has a certain contact killing effect. The chemical structure of spirotetramat is as follows:

[0003]

[0004] In the field of medicine, different solid forms of the same drug have obvious differences in melting point and dissolution performance, which even directly affect the bioavailability of the drug. Metastable crystals often become the dominant crystals in polymorphic systems due to their better solubility, dissolution and relative stability. Similarly, in the field of pesticides and insecticides, it has been reported that the contact activity of insecticides is negatively correlated with the thermodynamic stability of the polymorphs of insecticides. Metastable crystals achieve the effect of increasing the efficacy and reducing the use of such drugs with their better contact activity. CN109790115B discloses the crystal form I of spirotetramat, with a melting point of 145°C.

[0005] US006114374A discloses a method for preparing amorphous spirotetramat. Amorphous spirotetramat has poor stability, and the commercial crystalline form is crystalline form I, but the commercial crystalline form I has poor water solubility, uneven particle size, poor fluidity, and other problems.

[0006] The spirotetramat crystal form I described in CN109790115B has the problems of long preparation time, low yield, too small product particle size, further leading to difficulty in filtration and easy loss of drugs during washing.

[0007] Therefore, exploring and discovering the polymorphic form of spirotetramat and determining its thermodynamic stability are of great significance to the long-term application of spirotetramat, and at the same time enrich the family of tetronic acid derivative insecticides. Summary of the invention

[0008] The purpose of the present invention is to overcome the problems existing in the prior art of the existence of spirotetramat amorphous and crystal form I and the current situation that the production and preparation process is not green and environmentally friendly, and to provide a spirotetramat crystal form II, a preparation method of spirotetramat crystal form II, a pesticide composition and its application. Compared with the spirotetramat amorphous, the spirotetramat crystal form II of the present invention has excellent room temperature and humidity stability, accelerated stability, and mechanical stability, is easy to store, and has lower hygroscopicity in a high humidity environment of 95% RH. The preparation method thereof is time-consuming and has high yield, can save the time spent on filtering, washing, and drying, and the preparation process is solvent-free and green and environmentally friendly.

[0009] In order to achieve the above-mentioned object, the first aspect of the present invention provides a spirotetramat crystal form II, wherein the X-ray powder diffraction measured using Cu-Kα radiation has a characteristic peak at the diffraction angle expressed in 2θ degrees at the following positions:

[0010] 2θ=5.91±0.2°, 2θ=7.72±0.2°, 2θ=11.0±0.2°, 2θ=22.00±0.2°, 2θ=22.75±0.2°, 2θ=23.37±0.2°.

[0011] Preferably, the X-ray powder diffraction of the spirotetramat crystalline form II measured using Cu-Kα radiation also has characteristic peaks at the diffraction angle expressed in 2θ degrees at the following positions:

[0012] 2θ=8.28±0.2°, 2θ=12.35±0.2°, 2θ=14.34±0.2°, 2θ=15.91±0.2°, 2θ=17.2 4±0.2°, 2θ=19.36±0.2°, 2θ=27.39±0.2°, 2θ=27.98±0.2°, 2θ=28.89±0.2°.

[0013] Preferably, the single crystal of the spirotetramat crystal form II belongs to the monoclinic system, the space group is P21 / c, the unit cell parameters are a=16.15830(10), b=16.60270(10), c=16.97130(10), α=90°, β=112.8910(10)°, γ=90°, and the unit cell volume is Z=8.

[0014] Preferably, in the FT-IR spectrum, the spirotetramat crystal form II is at 2944 -1 , 1773 -1 ,1684 -1 ,1201 -1 ,1171 -1 , 1150 -1 and 1095cm -1 One or more wave numbers (cm-1 , ±0.2%) has a characteristic functional group vibration peak.

[0015] Preferably, the spirotetramat crystalline form II exhibits a melting point of 140.75±3° C. in the DSC curve.

[0016] Preferably, the spirotetramat crystalline form II exhibits a differential scanning calorimetry (DSC) curve with an endothermic melting peak of 73.49±10 J / g.

[0017] Preferably, the spirotetramat crystalline form II presents a thermal gravimetric analysis (TGA) curve with a decomposition temperature at 245.25±5°C.

[0018] In a second aspect of the present invention, a method for preparing spirotetramat crystalline form II is provided, wherein the method comprises the following steps:

[0019] 1) melting spirotetramat powder at 2-5° C. above its melting point;

[0020] 2) crystallizing the melted liquid at a temperature of 40-85° C. to obtain the spirotetramat crystal form II.

[0021] Preferably, in step 2), the crystallization temperature is 50-70°C.

[0022] The third aspect of the present invention provides a pesticide composition, which contains spirotetramat crystalline form II prepared by the method described in the second aspect of the present invention and at least one pesticide acceptable adjuvant.

[0023] Preferably, the auxiliary agent is selected from at least one of a surfactant, a liquid diluent, a solid diluent, a wetting agent, a dispersant, a thickener, an antifreeze agent and a biocide.

[0024] Preferably, the pesticide composition is in the form of any one of a suspension, a soluble liquid, a dispersible liquid, an emulsifiable concentrate, an emulsifiable seed dressing, a suspension seed dressing, a granule, a microgranule and a water-dispersible granule, preferably a suspension.

[0025] Preferably, the mass percentage of spirotetramat crystalline form II in the pesticide composition is 10-75%.

[0026] The fourth aspect of the present invention provides the use of the spirotetramat crystalline form II described in the first aspect of the present invention or the spirotetramat crystalline form II prepared by the method described in the second aspect of the present invention in the preparation of pest control.

[0027] Preferably, the harmful organisms include any one of aphids, thrips, mites, whiteflies, scale insects or mealybugs.

[0028] Preferably, the composition is used for controlling pests on cotton, potatoes, ornamental plants, fruit trees, vegetables, cucurbits, beets, bananas, apples, carrots, celery, citrus, pineapples and vines.

[0029] Through the above technical scheme, the spirotetramat crystalline form II of the present invention exhibits a lower melting point and melting enthalpy than the spirotetramat crystalline form I and is a metastable crystalline form, and the solubility of the spirotetramat crystalline form II in water at 30°C is 35 mg / L, which is higher than the solubility of the spirotetramat crystalline form I of 18 mg / L.

[0030] In addition, compared with the amorphous spirotetramat, the spirotetramat crystal form II of the present invention has excellent room temperature and humidity stability, accelerated stability, and mechanical stability, is easy to store, and has lower hygroscopicity in a high humidity environment of 95% RH. The preparation method thereof is time-saving and has high yield, and can save the time spent on filtering, washing, and drying. The preparation process is solvent-free and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is the X-ray diffraction pattern of spirotetramat crystalline form II in Example 1 of the present invention.

[0032] Figure 2 This is a single crystal structure diagram of spirotetramat crystalline form II prepared in Example 1 of the present invention obtained by single crystal analysis.

[0033] Figure 3 This is a unit cell stacking diagram of spirotetramat crystalline form II prepared in Example 1 of the present invention.

[0034] Figure 4 This is the theoretical powder XRD spectrum of spirotetramat crystalline form II prepared in Example 1 of the present invention calculated through single crystal structure.

[0035] Figure 5 This is the FT-IR spectrum of spirotetramat crystalline form II in Example 1 of the present invention.

[0036] Figure 6 This is a differential scanning calorimetry (DSC) graph of spirotetramat crystalline form II in Example 1 of the present invention.

[0037] Figure 7 This is the thermal gravimetric TGA graph of spirotetramat crystalline form II in Example 1 of the present invention.

[0038] Figure 8 It is the XRD powder diffraction spectrum of spirotetramat crystalline form II sampled during the normal temperature and humidity stability and accelerated stability experiments in Test Example 1 of the present invention.

[0039] Fig. 9 It is the XRD powder diffraction spectrum of spirotetramat crystalline form II in test example 2 of the present invention under different ball milling times.

[0040] Fig.10 This is the dynamic vapor adsorption DVS diagram of spirotetramat crystal form II in Test Example 3 of the present invention.

[0041] Fig.11 It is the XRD powder diffraction pattern of the amorphous spirotetramat in Comparative Example 1 of the present invention.

[0042] Fig.12 This is the dynamic vapor adsorption DVS diagram of spirotetramat crystal form I in comparative test example 1 of the present invention.

[0043] Fig.13 The crystal habit and XRD powder diffraction pattern of spirotetramat crystalline form I in comparative test example 2 of the present invention. DETAILED DESCRIPTION

[0044] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0045] According to a first aspect of the present invention, there is provided a spirotetramat crystalline form II, wherein the X-ray powder diffraction measured using Cu-Kα radiation has characteristic peaks at the following diffraction angles expressed in 2θ angles: 2θ=5.91±0.2°, 2θ=7.72±0.2°, 2θ=11.0±0.2°, 2θ=22.00±0.2°, 2θ=22.75±0.2°, 2θ=23.37±0.2°.

[0046] Preferably, the X-ray powder diffraction of the spirotetramat crystalline form II measured using Cu-Kα radiation also has characteristic peaks at the diffraction angles expressed in 2θ angles: 2θ=8.28±0.2°, 2θ=12.35±0.2°, 2θ=14.34±0.2°, 2θ=15.91±0.2°, 2θ=17.24±0.2°, 2θ=19.36±0.2°, 2θ=27.39±0.2°, 2θ=27.98±0.2°, 2θ=28.89±0.2°.

[0047] In the present invention, the method for measuring the X-ray diffraction patterns is as follows: all X-ray diffraction patterns are measured using powder diffraction in reflection geometry at room temperature using the following acquisition parameters (as shown in Table 1).

[0048] Table 1

[0049] MiniFlex600 from Rigaku, Japan; Temperature: Room temperature 25℃ Cu Kα radiation, 40 kV, 15 mA Step size: 0.01 degrees 2-theta Scanning range: 3-60 degrees 2-θ Scanning speed: 0.5° / min

[0050] According to the present invention, preferably, the single crystal of spirotetramat crystalline form II belongs to the monoclinic system, the space group is P21 / c, the unit cell parameters are a=16.15830(10), b=16.60270(10), c=16.97130(10), α=90°, β=112.8910(10)°, γ=90°, and the unit cell volume Z=8.

[0051] According to the present invention, the single crystal structure of the spirotetramat II crystal form is determined at 293K using a Rigaku Oxford Diffraction single crystal diffractometer and a graphite monochromatic diffractometer Cu Kα ray Data were collected by multi-layer scanning, and the data reduction and absorption correction were performed using the ShelXL (Sheldrick, 2015) program package. The space group was determined based on the extinction law of the system and verified by the refinement results. All crystal structures were solved by the direct method using ShelXL (Sheldrick, 2015), as shown in Table 2.

[0052] Table 2

[0053]

[0054] In the present invention, the method for determining the single crystal structure is: using the following parameters of a single crystal diffractometer (as shown in Table 3) to collect single crystal data of spirotetramat crystal form II and analyze the single crystal structure.

[0055] Table 3

[0056]

[0057] According to the present invention, preferably, in the FT-IR spectrum, the spirotetramat crystal form II is at 2944 -1 , 1773 -1 ,1684 -1 ,1201 -1 ,1171 -1 , 1150 -1 and 1095cm -1 One or more wave numbers (cm -1 , ±0.2%) has a characteristic functional group vibration peak.

[0058] In the present invention, the FT-IR measurement method is: all FT-IR spectra are measured using the following acquisition parameters (as shown in Table 4).

[0059] Table 4

[0060] FT-IR Spectrometer German Bruker Fourier infrared spectrometer ALPHA Wavelength range <![CDATA[400-4000cm -1 ]]> Resolution <![CDATA[4cm -1 ]]> Scan times 16

[0061] According to the present invention, the solubility of spirotetramat crystal form II in water at 30° C. is 35 mg / L, which is a pesticide crystal form that is poorly soluble in water.

[0062] According to the present invention, preferably, the spirotetramat crystalline form II exhibits a melting point of 140.75±3°C in the DSC curve; preferably, the spirotetramat crystalline form II exhibits an endothermic melting peak of 73.49±10 J / g in the DSC curve.

[0063] In the present invention, the method for determining the DSC thermogram is as follows: all DSC thermograms are obtained using the following acquisition parameters (as shown in Table 5).

[0064] Table 5

[0065] Differential Scanning Calorimeter Mettler Toledo DSC1 / 500 Heating rate 10mL / min scope 30℃-200℃

[0066] According to the present invention, preferably, the spirotetramat crystalline form II exhibits a decomposition temperature of 245.25±5° C. in a thermal gravimetric analysis (TGA) curve.

[0067] In the present invention, the method for determining the TGA thermogram is as follows: In the present invention, the following acquisition parameters (as shown in Table 6) are used to obtain all TGA thermograms.

[0068] Table 6

[0069] Thermogravimetric Analyzer Mettler Toledo TGA / DSC 1 / SF; Heating rate 10mL / min scope 25℃-300℃

[0070] According to the present invention, the spirotetramat crystal form II has lower hygroscopicity in a high humidity environment of 95% RH.

[0071] In the present invention, the method for determining the DVS adsorption and desorption spectra is as follows: all DVS adsorption and desorption spectra are obtained using the following acquisition parameters (as shown in Table 7).

[0072] Table 7

[0073] Dynamic Vapor Sorption Analyzer Surface Measurement Systems,DVS Adventure; temperature 25℃ Maximum balancing time 120min Step Length 5%RH Humidity cycle range 0-95-0%RH

[0074] According to the present invention, spirotetramat crystalline form II is prepared by essentially Figure 1 characterized by an X-ray powder diffraction pattern as shown in, and / or by substantially Figure 5 , and / or by substantially the same Figure 6 , and / or by substantially the same Figure 7 The TGA differential thermal spectrum shown in .

[0075] According to a second aspect of the present invention, a method for preparing spirotetramat crystalline form II is provided, wherein the method comprises the following steps:

[0076] 1) melting spirotetramat powder at 2-5° C. above its melting point;

[0077] 2) crystallizing the melted liquid at a temperature of 40-85° C. to obtain the spirotetramat crystal form II.

[0078] According to the present invention, preferably, the crystallization temperature is 50-70°C.

[0079] According to the present invention, the crystallization time may be 10-720 min; preferably, the crystallization time is 45-360 min.

[0080] According to the present invention, in order to promote or accelerate the crystallization in step 2), step 2) further comprises the step of adding seed crystals or a promoter to accelerate the crystallization.

[0081] According to the present invention, in order to have a better accelerated crystallization effect, the amount of the seed crystal added can be 0.01-2 weight % based on the weight of the spirotetramat powder; preferably, the amount of the seed crystal added is 0.01-1 weight %; more preferably, the amount of the seed crystal added is 0.05-0.5 weight %.

[0082] According to the present invention, in order to have a better effect of accelerating crystallization, the amount of the promoter added may be 0.01-2% by weight based on the weight of the spirotetramat powder; preferably, the amount of the promoter added is 0.01-1% by weight based on the weight of the spirotetramat powder; more preferably, the amount of the promoter added is 0.05-0.5% by weight based on the weight of the spirotetramat powder.

[0083] According to the present invention, the accelerator is a polymer accelerator, preferably at least one of polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide and hydroxypropyl methylcellulose.

[0084] In a preferred embodiment of the present invention, spirotetramat crystal form II is prepared by adding a promoter (preferably polyvinyl pyrrolidone) to the molten liquid at the initial set temperature in step 2) during crystallization.

[0085] According to the third aspect of the present invention, a pesticide composition is provided, which contains the spirotetramat crystalline form II described in the first aspect of the present invention or the spirotetramat crystalline form II prepared by the preparation method described in the second aspect of the present invention and at least one pesticide-acceptable adjuvant.

[0086] According to the present invention, the mass percentage of spirotetramat crystalline form II in the pesticide composition may be 10-75 weight %; preferably, the mass percentage of spirotetramat crystalline form II in the composition is 10-50 weight %; more preferably, the mass percentage of spirotetramat crystalline form II in the composition is 20-30 weight %.

[0087] According to the present invention, in order to ensure good dispersibility, suspension rate and storage stability of the pesticide formulation, the pesticide acceptable adjuvant is selected from at least one of a surfactant, a liquid diluent, a solid diluent, a wetting agent, a dispersant, a thickener, an antifreeze agent and a biocide.

[0088] According to the present invention, for the purpose of making the pesticide formulation green and environmentally friendly, the formulation of the composition is any one of a suspension, a soluble liquid, a dispersible liquid, an emulsifiable concentrate, an emulsion seed dressing, a suspension seed dressing, a granule, a microgranule and a water-dispersible granule, preferably a suspension.

[0089] According to a fourth aspect of the present invention, there is provided use of the pesticide composition described in the third aspect of the present invention in controlling harmful organisms.

[0090] In the present invention, the use of spirotetramat as an insecticide is well known in the art and is used on a commercial scale. Therefore, the techniques known in the art for the preparation of amorphous spirotetramat and crystalline form I and the application of spirotetramat can also be applied in a similar manner to the spirotetramat in crystalline form II of the present invention.

[0091] According to the present invention, in order for the spirotetramat crystalline form II to be present in a concentration sufficient to achieve the desired dosage when applied to plants or their loci, preferably, the spirotetramat crystalline form II is present in a concentration of about 1% to about 75% by weight of the total mixture. For example, by incorporating water and a carrier into the spirotetramat crystalline form II, an emulsifier and / or a dispersant and / or other adjuvants may also be used to prepare the formulation.

[0092] According to the present invention, the harmful organisms include any one of aphids, thrips, mites, whiteflies, scale insects or mealybugs; preferably, the composition is used to control harmful organisms on cotton, potatoes, ornamental plants, fruit trees, vegetables, cucurbits, beets, bananas, apples, carrots, celery, citrus, pineapples or vines.

[0093] The present invention is described in detail below by way of examples, but the present invention is not limited to the following examples.

[0094] In the following examples, the determination method of spirotetramat crystalline form II is as follows.

[0095] 1) The following single crystal diffractometer parameters were used to collect single crystal data of spirotetramat Form II and to analyze the single crystal structure:

[0096]

[0097] 2) All X-ray diffraction patterns were determined using powder diffraction in reflection geometry at room temperature using the following acquisition parameters:

[0098] MiniFlex600 from Rigaku, Japan; Temperature: Room temperature 25℃ Cu Kα radiation, 40 kV, 15 mA Step size: 0.01 degrees 2-theta Scanning range: 3-60 degrees 2-θ Scanning speed: 0.5° / min

[0099] 3) For crystallized samples, use 4 cm -1 The IR spectrum was measured with a resolution of 16 scans. Figure 5 2944 shown -1 , 1773 -1 ,1684 -1 ,1201 -1 ,1171 -1 , 1150 -1 and 1095cm -1 One or more wave numbers (cm -1 , ±0.2%) to identify the spirotetramat crystalline form II.

[0100] All FT-IR spectra were acquired using the following parameters:

[0101] FT-IR Spectrometer German Bruker Fourier infrared spectrometer ALPHA Wavelength range <![CDATA[400-4000cm -1 ]]> Resolution <![CDATA[4cm -1 ]]> Scan times 16

[0102] 4) All DSC thermograms were acquired using the following acquisition parameters:

[0103] Differential Scanning Calorimeter Mettler Toledo DSC1 / 500 Heating rate 10mL / min scope 30℃-200℃

[0104] 5) All TGA thermograms were acquired using the following acquisition parameters:

[0105]

[0106] 6) All DVS adsorption and desorption spectra were acquired using the following acquisition parameters:

[0107] Dynamic Vapor Sorption Analyzer Surface Measurement Systems, DVS Adventure; temperature 25℃ Maximum balancing time 120min Step Length 5%RH Humidity cycle range 0-95-0%RH

[0108] Example 1

[0109] Preparation method of spirotetramat crystal form II (85°C):

[0110] 500 mg of spirotetramat crystal form I was placed on a heating table and heated to 147° C. until it was completely melted into a molten liquid. The molten liquid was transferred to an ambient temperature of 85° C. and crystals began to emerge after standing for 1 hour. That is, the crystals were spirotetramat crystal form II. The final product was weighed, and the yield was 99.7%.

[0111] The spirotetramat crystals obtained in Example 1 were characterized by X-ray powder diffraction (abbreviated as "XRD"), and the spectrum is shown in Figure 1 The 2θ (±0.2°) characteristic peaks in the XRD spectrum are located at 5.91, 7.72, 11.00, 21.99, 22.75 and 23.37 degrees. Specifically, Figure 1 The diffraction spectrum of spirotetramat crystalline form II is summarized in Table 8:

[0112] Table 8

[0113] 2θ Diffraction intensity 2θ Diffraction intensity 5.91±0.2° 15374 19.36±0.2° 128922 7.72±0.2° 61270 22.00±0.2° 158326 8.28±0.2° 32329 22.75±0.2° 256261 11.0±0.2° 69092 23.37±0.2° 105811 12.35±0.2° 112538 27.39±0.2° 46031 14.34±0.2° 118862 27.98±0.2° 27287 15.91±0.2° 123801 28.89±0.2° 45477 17.24±0.2° 110610

[0114] The monomer structure of spirotetramat crystal form II obtained by single crystal analysis is shown in Figure 2 . Figure 3 This is the unit cell stacking diagram of spirotetramat crystal form II of this example. Figure 4 This is the theoretical powder diffraction pattern of spirotetramat crystalline form II of this example calculated by single crystal structure. Figure 2 It can be seen that the crystal is a pure crystal form of spirotetramat; Figure 3 It can be seen that hydrogen-bonded dimers are formed between the molecules of spirotetramat crystal form II, and adjacent dimers are stacked and extended through weak interactions; Figure 4 It can be seen that the powder XRD results are highly consistent with the theoretical powder diffraction pattern calculated from the single crystal structure.

[0115] Figure 5 The spirotetramat crystal form II of this embodiment is shown to be about 2944 -1 , 1773 -1 ,1684 -1 ,1201 -1 ,1171 -1 , 1150 -1 and 1095cm -1 Multiple wave numbers (cm -1 , ±0.2%) with characteristic functional group vibration peaks.

[0116] Figure 6 The differential scanning calorimetry ("XRD") spectrum of the spirotetramat crystal form II of this embodiment is shown. The results show that there is an obvious endothermic melting peak at a peak value of 140.75°C. The peak value and the melting enthalpy are lower than the 145°C peak value and 91J / g melting enthalpy of the crystal form I reported in the CN109790115B patent, indicating that the crystal form II is metastable relative to the crystal form I.

[0117] Figure 7 The thermogravimetric analysis (TGA) spectrum of the crystal form shows a decomposition peak at 245.25°C, indicating that it is a pure crystal form.

[0118] Example 2

[0119] Preparation method of spirotetramat crystal form II (60°C):

[0120] 500 mg of spirotetramat crystal form I was placed on a heating table and heated to 147° C. until it was completely melted into a molten liquid. The molten liquid was transferred to an ambient temperature of 60° C. and crystals began to emerge after standing for 2 hours. That is, the crystals were spirotetramat crystal form II. The final product was weighed, and the yield was 99.8%.

[0121] The spirotetramat crystals obtained in Example 2 were tested using the same testing method as in Example 1. It was found that the obtained product was the same crystal form II as in Example 1, and the DSC spectrum was also substantially the same as in Example 1.

[0122] Example 3

[0123] Preparation method of spirotetramat crystal form II (40°C):

[0124] 500 mg of spirotetramat crystal form I was placed on a heating table and heated to 147° C. until it was completely melted into a molten liquid. The molten liquid was transferred to an ambient temperature of 40° C. and crystals began to form after standing for 24 hours. That is, the crystals were spirotetramat crystal form II. The final product was weighed, and the yield was 99.68%.

[0125] The spirotetramat crystals obtained in Example 3 were tested using the same testing method as in Example 1. It was found that the obtained product was the same crystal form II as in Example 1, and the DSC spectrum was also substantially the same as in Example 1.

[0126] Example 4

[0127] Preparation method of spirotetramat crystal form II (adding seed crystals):

[0128] 500 mg of spirotetramat crystal form I was placed on a heating table and heated to 147° C. until it was completely melted into a molten liquid. The molten liquid was transferred to an ambient temperature of 85° C., and the molten liquid became viscous. After adding 0.5 wt % of spirotetramat crystal form II seed crystals, crystals were immediately produced, i.e., the crystals were spirotetramat crystal form II. The weight of the final product was weighed, and the yield was 99.74%.

[0129] The spirotetramat crystals obtained in Example 4 were tested using the same testing method as in Example 1. It was found that the obtained product was the same crystal form II as in Example 1, and the DSC spectrum was also substantially the same as in Example 1.

[0130] Example 5

[0131] Preparation method of spirotetramat crystal form II (adding polyvinyl pyrrolidone molecular weight 8000):

[0132] 500 mg of spirotetramat crystal form I was placed on a heating table and heated to 147° C. until it was completely melted into a molten liquid. The molten liquid was transferred to an ambient temperature of 85° C., and the molten liquid became viscous. After adding 0.5 wt % of polyvinyl pyrrolidone with a molecular weight of 8000, crystals were immediately produced, that is, the crystals were spirotetramat crystal form II. The weight of the final product was weighed, and the yield was 99.6%.

[0133] The spirotetramat crystals obtained in Example 5 were tested using the same testing method as in Example 1. It was found that the obtained product was the same crystal form II as in Example 1, and the DSC spectrum was also substantially the same as in Example 1.

[0134] Example 6

[0135] Preparation of spirotetramat crystal form II water-based suspension (SC):

[0136] The spirotetramat crystalline form II obtained in Examples 1-5 was mixed uniformly as an active component with other adjuvants and water according to the proportions in Table 9, and then pre-dispersed using a high shear emulsifier and then wet-milled by a nano grinder to stably obtain a multiphase dispersion system with a particle size of about 5 μm, forming a water-based suspension (SC) of spirotetramat crystalline form II.

[0137] Table 9

[0138] Components content% Function Spirotetramat Crystal Form II 14.5 Active ingredients Sodium alkylnaphthalene sulfonate-formaldehyde condensate (MORWET D-425) 3 Dispersants Polyalkylene glycol ether (ATLASTMG-5000) 2 Wetting Agents Butylated Hydroxybenzene (BHT) 1 Antioxidants Modified polydimethylsiloxane formulation (SAG 1572) 0.2 Defoaming agent Propylene glycol 8 antifreeze Xanthan gum 0.2 Thickener water Top up to 100 filler

[0139] Test Example 1

[0140] Room temperature and humidity stability and accelerated stability of spirotetramat crystal form II:

[0141] 1 g of spirotetramat crystal form II was divided into two parts, and placed under 25°C / 50%RH and 40°C / 75%RH conditions for 0 day, 7 days, 35 days, 60 days, and 90 days, respectively.

[0142] The spirotetramat crystals in Example 1 were sampled according to the storage date and measured by PXRD diffraction. Figure 8 It can be seen that the obtained spirotetramat crystal form II can exist stably. Similarly, the spirotetramat crystal form II obtained in Example 2-5 was measured, and the product obtained in Example 2-5 can also exist stably.

[0143] Test Example 2

[0144] Mechanical stability of spirotetramat crystal form II:

[0145] 500 mg of spirotetramat crystalline form II was placed in a ball mill and ball milled at 20 Hz. Samples were taken for analysis after 0 h, 1 h, 2 h, 3 h, and 4 h, respectively.

[0146] The spirotetramat powder in Example 1 was sampled after each ball milling time and measured by PXRD diffraction. Fig. 9 It can be seen that the obtained spirotetramat crystal form II can be stably present under mechanical grinding. Similarly, the spirotetramat crystal form II obtained in Example 2-5 was measured, and the spirotetramat crystal form II obtained in Example 2-5 can be stably present under mechanical grinding.

[0147] Test Example 3

[0148] Hygroscopicity of spirotetramat II crystal form:

[0149] About 10 mg of spirotetramat crystalline form II was weighed and pre-dried at 25°C with a dry nitrogen gas flow; humidity cycle range: relative humidity increased from 0% to 95% in a certain step length, and then dropped back to 0%; step value: 5% relative humidity; weight gain balance standard: set the weight change rate (d m / d t ) is less than 0.01% and is considered balanced; the longest equilibrium time is 120 min. The weight change is calculated using the corresponding dry sample. The results are shown in Fig.10 shown.

[0150] The DVS spectrum analysis of the spirotetramat crystal form II in Example 1 shows that when the relative humidity reaches 95%, the moisture absorption of the drug is 0.79%, which is slightly hygroscopic. Similarly, the spirotetramat crystal form II obtained in Examples 2-5 was measured. The spirotetramat crystal form II obtained in Example 2 absorbed 0.75% of moisture when the relative humidity reached 95%; the spirotetramat crystal form II obtained in Example 3 absorbed 0.72% of moisture when the relative humidity reached 95%; the spirotetramat crystal form II obtained in Example 4 absorbed 0.76% of moisture when the relative humidity reached 95%; the spirotetramat crystal form II obtained in Example 5 absorbed 0.68% of moisture when the relative humidity reached 95%. These products are all slightly hygroscopic.

[0151] Comparative Example 1

[0152] Preparation of spirotetramat amorphous form:

[0153] 500 mg of spirotetramat crystalline form I was placed on a heating table and heated to 147°C until it was completely melted into a molten liquid. The molten liquid was transferred to a low-temperature environment of 10°C and allowed to stand for 24 hours before sampling for X-ray powder diffraction (abbreviated as "XRD") characterization. The spectrum is shown in Fig.11 , is amorphous.

[0154] Comparative test example 1

[0155] Hygroscopicity of spirotetramat crystal form I:

[0156] About 10 mg of spirotetramat crystalline form I was weighed and pre-dried at 25°C with a dry nitrogen gas flow; humidity cycle range: relative humidity increased from 0% to 95% in a certain step length, and then dropped back to 0%; step value: 5% relative humidity; weight gain balance standard: set the weight change rate (d m / d t ) is less than 0.01% and is considered balanced; the longest equilibrium time is 120 minutes. The weight change is calculated using the corresponding dry sample. The results are as follows Fig.12 When the relative humidity reaches 95%, the weight change rate of the drug is about 1.1%, which is greater than the weight gain rate of Form II. Compared with Form II, under the extreme condition of 95% RH, the hygroscopicity of the drug is stronger than that of Form II.

[0157] Comparative test example 2

[0158] Preparation method of spirotetramat crystal form I:

[0159] According to the preparation method of spirotetramat crystal form I in patent CN109790115B, 1g of spirotetramat crystal form I sample was placed in a 20mL glass bottle together with 10mL of methanol, and the resulting slurry was heated to 64°C to obtain a uniform solution. The resulting hot solution was stirred at 64°C for 2h, and the crystal form I was completely dissolved. The resulting solution was slowly cooled (1°C / min) to 24°C. During cooling, no crystals were produced, and the resulting heterogeneous mixture was stirred at 10°C to 20°C for 4h. Then, the slurry was filtered and washed with 10mL of chilled methanol, and the filtered crystals were vacuum dried at 45°C. XRD powder diffraction analysis showed that the crystal form was spirotetramat crystal form I. Fig.13 .

[0160] The product yield of this process is calculated to be very low at 2.17%. The product presents small crystals with irregular morphology, is slow to filter, and generates electrostatic adsorption agglomeration after drying.

[0161] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A spirotetramat crystal form II, characterized in that: The X-ray powder diffraction measured using Cu-Kα radiation has characteristic peaks at diffraction angles expressed in degrees 2θ at the following locations: 2θ=5.91±0.2°, 2θ=7.72±0.2°, 2θ=11.0±0.2°, 2θ=22.00±0.2°, 2θ=22.75±0.2°, 2θ=23.37±0.2°.

2. The spirotetramat crystal form II according to claim 1, wherein The X-ray powder diffraction of the spirotetramat crystalline form II measured using Cu-Kα radiation also has characteristic peaks at the following diffraction angles expressed in 2θ degrees: 2θ=8.28±0.2°, 2θ=12.35±0.2°, 2θ=14.34±0.2°, 2θ=15.91±0.2°, 2θ=17.2 4±0.2°, 2θ=19.36±0.2°, 2θ=27.39±0.2°, 2θ=27.98±0.2°, 2θ=28.89±0.2°; Preferably, the single crystal of the spirotetramat crystal form II belongs to the monoclinic system, the space group is P21 / c, the unit cell parameters are a=16.15830(10), b=16.60270(10), c=16.97130(10), α=90°, β=112.8910(10)°, γ=90°, and the unit cell volume is Z=8.

3. The spirotetramat crystalline form II according to claim 1, wherein In the FT-IR spectrum, the spirotetramat crystal form II is at 2944 -1 , 1773 -1 ,1684 -1 ,1201 -1 ,1171 -1 , 1150 -1 and 1095cm -1 One or more wave numbers (cm -1 , ±0.2%) has a characteristic functional group vibration peak.

4. The spirotetramat crystalline form II according to claim 1, wherein The spirotetramat crystal form II exhibits a melting point of 140.75±3°C in the DSC curve; Preferably, the spirotetramat crystalline form II exhibits a differential scanning calorimetry curve with an endothermic melting peak of 73.49±10 J / g; Preferably, the spirotetramat crystalline form II presents a thermal gravimetric curve with a decomposition temperature at 245.25±5°C.

5. A method for preparing spirotetramat crystal form II, characterized in that: The method comprises the following steps: 1) melting spirotetramat powder at 2-5° C. above its melting point; 2) crystallizing the melted liquid at a temperature of 40-85° C. to obtain the spirotetramat crystal form II.

6. The method according to claim 5, wherein in step 2), the crystallization temperature is 50-70°C.

7. A pesticide composition, characterized in that: The composition contains the spirotetramat crystalline form II according to any one of claims 1 to 4 and at least one pesticide-acceptable adjuvant.

8. The composition according to claim 7, wherein The auxiliary agent is selected from at least one of a surfactant, a liquid diluent, a solid diluent, a wetting agent, a dispersant, a thickener, an antifreeze agent and a biocide.

9. The composition according to claim 7, wherein The composition is in the form of any one of a suspension, a soluble liquid, a dispersible liquid, an emulsifiable concentrate, an emulsifiable seed dressing, a suspension seed dressing, a granule, a microgranule and a water-dispersible granule, preferably a suspension.

10. The composition according to claim 7, wherein The mass percentage of spirotetramat crystal form II in the composition is 10-75%.

11. Use of the composition according to claim 7 in controlling harmful organisms.

12. The use according to claim 11, wherein: The harmful organisms include any one of aphids, thrips, mites, whiteflies, scale insects or mealybugs; Preferably, the composition is used for controlling pests on cotton, potatoes, ornamental plants, fruit trees, vegetables, cucurbits, beets, bananas, apples, carrots, celery, citrus, pineapples or vines.

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