CN111187204A - Acetamiprid eutectic crystal and preparation method and application thereof - Google Patents
Acetamiprid eutectic crystal and preparation method and application thereof Download PDFInfo
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- CN111187204A CN111187204A CN202010029719.3A CN202010029719A CN111187204A CN 111187204 A CN111187204 A CN 111187204A CN 202010029719 A CN202010029719 A CN 202010029719A CN 111187204 A CN111187204 A CN 111187204A
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
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Abstract
The invention relates to the field of compound crystal forms, in particular to an acetamiprid eutectic and a preparation method and application thereof, wherein the acetamiprid eutectic comprises the following components: acetamiprid (acetamiprid) and organic acids; wherein the molar ratio of the acetamiprid (acetamiprid) to the organic acid is 10: 1-1: 10; the invention also provides a preparation method and application of the acetamiprid eutectic. According to the technical scheme, organic acids such as acetic acid, oxalic acid or malonic acid are used as eutectic formers to form eutectic with acetamiprid, so that the acetamiprid eutectic crystal has the advantages of high melting point, high water solubility value and high water solubility rate, and is suitable for being applied to the production process of pesticide preparations.
Description
Technical Field
The invention belongs to the field of compound crystal forms, and particularly relates to an acetamiprid eutectic, and a preparation method and application of the eutectic.
Background
In the field of agricultural chemistry, different solid forms of compounds have different physicochemical properties, such as melting point, density, powder flowability and the like, which all affect the preparation process and quality of preparation products, and even affect the effects on crops and plant diseases and insect pests after application, so the selection of the solid form of the compound is one of the factors to be considered in the research of pesticide preparations. The solid form of the compound mainly comprises different crystal forms, salts, hydrates or solvates and eutectic crystals. A co-crystal, which generally refers to a crystal in which the active ingredient and the co-crystal former are bound by hydrogen bonding or other non-covalent bonds, is a multicomponent crystal. The eutectic is essentially a supramolecular self-assembly system, and is a balanced result of thermodynamics, kinetics and molecular recognition. During the process of molecular self-assembly, intermolecular interactions and steric effects influence the formation of supramolecular networks, which in turn directly influence the crystal formation. Within the eutectic system, the interactions between different molecules are mainly hydrogen bonding, pi-pi stacking, van der waals forces and halogen bases. The physical and chemical properties of the eutectic can be changed without changing the covalent structure of the drug, and compared with a single crystal form, the eutectic can greatly change the properties of the compound due to the introduced different components, so that the properties of the compound can be adjusted in different properties.
Acetamiprid is a neonicotinoid compound successfully researched and developed by Nippon Caoda corporation, in particular to a nicotinamide acetylcholine receptor stimulant, is a systemic pesticide, has interlayer conduction activity and contact killing and stomach poisoning effects, is used for preventing and treating hemiptera (especially aphid), thysanoptera and lepidoptera pests, is widely applicable to crops, and is particularly suitable for vegetables, fruit trees and tea trees. However, acetamiprid has a melting point of 98.9 ℃, and is slowly decomposed at a pH of 9 and 45 ℃, and is easily mixed with impurities due to melting or degraded during hot melting in the process of preparing certain specific preparations (such as granules). In addition, the water solubility of the acetamiprid is poor, and is only 4250mg/L (25 ℃), the phenomenon of austenite ripening is easy to occur in the storage process (especially above 35 ℃) of the acetamiprid preparation, especially the aqueous suspension, and the effective components can settle over time and even influence the final use performance. Therefore, the disadvantages of low water solubility and low melting point are always troubling the application of the compound in agriculture. The existing common method for changing the property of the product generally needs to change the structure, add an auxiliary agent and other modes, so that the cost is high, and the performance of the actual application of the product is influenced due to the change of the structure of part of the modes.
Basf european corporation disclosed a crystalline complex of 4-hydroxybenzoic acid and a selected pesticide in patent application No. CN201080050233.2, and specifically disclosed a crystalline complex of 4-hydroxybenzoic acid and acetamiprid (i.e., acetamiprid), it is known from the disclosure of this patent application that the crystalline complex of 4-hydroxybenzoic acid and acetamiprid had a melting point of about 126.1 ℃, a water solubility value of 1890mg/L at room temperature, and that seeds treated with the acetamiprid-co-crystal showed an increase in germination of 8%. The patent application No. CN200810116936.5 of Jiangsuchun group corporation discloses an organic salt obtained by combining salicylic acid with pymetrozine or acetamiprid, but only discloses the safety and efficacy of pymetrozine salicylate, and does not examine the organic salt obtained by combining acetamiprid and salicylic acid.
The applicant unexpectedly finds that by utilizing the eutectic mode, on the premise of not changing the covalent structure of the acetamiprid, the acetamiprid eutectic is prepared by combining the acetamiprid with carboxylic acids such as oxalic acid and malonic acid, so that the physicochemical properties of the acetamiprid can be effectively improved, the water solubility and the melting point of the acetamiprid are improved, the stability and the processability of the acetamiprid are enhanced, and a foundation is laid for the further development and application of the acetamiprid.
Disclosure of Invention
The invention aims to overcome the inconvenience caused by the lower water solubility and the lower melting point of the acetamiprid in the prior art in the preparation and storage processes of pesticide preparations. The method for changing the property of the acetamiprid has the advantages of high melting point, high water solubility value and high water solubility rate, and is suitable for being applied to the production process of pesticide preparations.
In order to achieve the technical purpose, the invention provides the following technical scheme: an acetamiprid cocrystal, comprising: acetamiprid (acetamiprid) and organic acids; wherein the molar ratio of the acetamiprid (acetamiprid) to the organic acid is 10: 1-1: 10;
further, the organic acid is a carboxylic acid; preferably any one of acetic acid, oxalic acid or malonic acid; oxalic acid is further preferable;
further, the molar ratio of the acetamiprid to the organic acid is 5: 1-1: 5; the preferable molar ratio is 3: 1-1: 3; still more preferred molar ratios are from 2:1 to 1: 2;
further, the pesticide composition comprises acetamiprid (acetamiprid) and oxalic acid, wherein the molar ratio of the acetamiprid to the oxalic acid is 1: 1-1: 2; the preferred molar ratio is 1: 1;
further, the acetamiprid (acetamiprid) comprises acetamiprid technical product, single crystal form of acetamiprid, a mixture of different crystal forms of acetamiprid, an amorphous acetamiprid substance, an acetamiprid solvate or a mixture of amorphous and crystal forms of acetamiprid;
further, at least 4 of the following diffraction peaks given in 2 θ values are shown in the spectrum: 7.591 degrees +/-0.2, 11.386 degrees +/-0.2, 12.834 degrees +/-0.2, 13.202 degrees +/-0.2, 15.120 degrees +/-0.2, 18.180 degrees +/-0.2, 19.181 degrees +/-0.2, 19.998 degrees +/-0.2, 20.955 degrees +/-0.2, 21.915 degrees +/-0.2, 22.670 degrees +/-0.2, 23.752 degrees +/-0.2, 24.731 degrees +/-0.2, 26.284 degrees +/-0.2, 27.404 degrees +/-0.2, 27.729 degrees +/-0.2 and 30.444 degrees +/-0.2;
still further, at least 5, usually at least 6, in particular all of the above diffraction peaks given as 2 θ values are shown in the spectrum;
still further, at least 4, in particular at least 5, usually at least 6, in particular all of the following diffraction peaks given as 2 θ values are shown in the spectrum: 7.591 degrees +/-0.1, 11.386 degrees +/-0.1, 12.834 degrees +/-0.1, 13.202 degrees +/-0.1, 15.120 degrees +/-0.1, 18.180 degrees +/-0.1, 19.181 degrees +/-0.1, 19.998 degrees +/-0.1, 20.955 degrees +/-0.1, 21.915 degrees +/-0.1, 22.670 degrees +/-0.1, 23.752 degrees +/-0.1, 24.731 degrees +/-0.1, 26.284 degrees +/-0.1, 27.404 degrees +/-0.1, 27.729 degrees +/-0.1 and 30.444 degrees +/-0.1;
still further, at least 4, in particular at least 5, usually at least 6, in particular all of the following diffraction peaks given as 2 θ values are shown in the spectrum: 7.591 °, 11.386 °, 12.834 °, 13.202 °, 15.120 °, 18.180 °, 19.181 °, 19.998 °, 20.955 °, 21.915 °, 22.670 °, 23.752 °, 24.731 °, 26.284 °, 27.404 °, 27.729 °, 30.444 °.
The invention also provides a preparation method of the cocrystal, which comprises the steps of mixing acetamiprid and organic acid, adding an alcohol solvent, stirring under heating or non-heating conditions, filtering, standing the filtrate, and collecting a solid as the cocrystal;
further, the organic acid is a carboxylic acid; still further, any one of acetic acid, oxalic acid or malonic acid; still further, oxalic acid or malonic acid; still further, oxalic acid;
the heating condition is heating at 30-50 ℃;
the alcohol solvent is any one or a mixture of methanol, ethanol, propanol or butanol; preferably methanol or ethanol;
further, adding an alcohol solvent, stirring for 2-4h under a heating condition, and filtering;
further, standing the filtrate for 3-5 days;
further, the solid-to-liquid ratio of the mixture of the acetamiprid and the organic acid to the alcohol solvent is (0.3-0.4) g, (3-4) mL;
still further, the solid-to-liquid ratio of the mixture of the acetamiprid and the organic acid to the alcohol solvent is (0.311-0.313) g, (3-4) mL;
further, the preparation method of the eutectic specifically comprises the following steps: mixing acetamiprid and oxalic acid, adding methanol, heating in a water bath at 50 ℃, stirring for 2-4h, filtering, standing and volatilizing the filtrate for 3-5 days, and collecting a solid as the eutectic;
or mixing acetamiprid and oxalic acid, adding ethanol, heating in water bath at 50 deg.C, stirring for 2-4 hr, filtering, standing the filtrate for volatilizing for 3-5 days, and collecting solid as the co-crystal;
still further, the filtration is hot filtration.
The invention also provides an agricultural formulation comprising an effective amount of an acetamiprid cocrystal as described above; preferably, the composition also comprises an agriculturally acceptable preparation carrier or a preparation auxiliary agent.
The present invention also provides a method for controlling pests, which comprises applying a pesticidally effective amount of the acetamiprid cocrystal as described above or the agricultural formulation as described above to the pests and/or their habitat.
The invention also provides the use of an acetamiprid cocrystal as described above or an agricultural formulation as described above for controlling pests.
Due to the adoption of the technology, compared with the prior art, the invention has the remarkable advantages that:
1) according to the technical scheme, carboxylic acids such as acetic acid, oxalic acid and malonic acid are used as eutectic formers and form eutectic with acetamiprid, so that the acetamiprid eutectic crystal has the advantages of high melting point, high water solubility and high water solubility rate, particularly the melting point is increased to 142.5 ℃, the water solubility is increased to 7.4g/L, the water solubility rate is greatly increased, the acetamiprid eutectic crystal is suitable for being applied to the production process of pesticide preparations, and the inconvenience caused by the low water solubility and the low melting point of the acetamiprid in the prior art in the preparation and storage processes of the pesticide preparations is solved;
2) according to the preparation method of the acetamiprid-oxalic acid eutectic, the solvent volatilization method and the cooling method are adopted to prepare the high-purity eutectic, and PXRD, melting point measurement and other related characterization and dissolution rate tests are performed on the eutectic, so that the prepared acetamiprid-oxalic acid eutectic has high purity and crystallinity, can be kept stable for a long time without deterioration, is simple in preparation process and low in cost, and is suitable for large-scale production.
Drawings
FIG. 1 is a PXRD spectrum of acetamiprid-oxalic acid eutectic prepared in example 1 of the present invention;
FIG. 2 is a comparison graph of PXRD spectra of acetamiprid-oxalic acid eutectic, acetamiprid and oxalic acid;
FIG. 3 is a comparison graph of dissolution rates of acetamiprid-oxalic acid eutectic and acetamiprid in physiological saline.
Detailed Description
In order to make the technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
Example 1
The preparation method of the acetamiprid-oxalic acid eutectic crystal is implemented according to the following steps:
putting mixed powder of 2.226g of acetamiprid raw material medicine and 0.900g of oxalic acid into a round-bottom flask according to the molar ratio of 1:1, adding 50mL of methanol into the round-bottom flask, heating and stirring the mixed powder and the methanol in a water bath at 30 ℃ for 2h, filtering, standing and volatilizing the filtrate for 3 days, and collecting a solid phase substance to obtain acetamiprid-oxalic acid eutectic and white crystal powder, wherein the solid phase substance is measured by using a D8 type X-ray diffractometer manufactured by BRUKER company of Germany under the test conditions of 40kV target tube voltage of a Cu-K α target, 10mA tube current and 2 degrees/min scanning speed, and the PXRD diffraction pattern of the product is shown in figure 1.
The characteristic diffraction peaks of PXRD of the acetamiprid-oxalic acid eutectic of the embodiment appear at 7.591 degrees, 11.386 degrees, 12.834 degrees, 13.202 degrees, 15.120 degrees, 18.180 degrees, 19.181 degrees, 19.998 degrees, 20.955 degrees, 21.915 degrees, 22.670 degrees, 23.752 degrees, 24.731 degrees, 26.284 degrees, 27.404 degrees, 27.729 degrees and 30.444 degrees. As shown in fig. 2, when compared with PXRD of acetamiprid bulk drug and oxalic acid bulk drug, the obtained acetamiprid-oxalic acid eutectic has significant changes in characteristic diffraction peak position and diffraction intensity, indicating that a new phase is generated.
Example 2
The preparation method of the acetamiprid-oxalic acid eutectic crystal is implemented according to the following steps:
putting mixed powder of 0.222g of acetamiprid raw material medicine and 0.090g of oxalic acid into a round-bottom flask according to the molar ratio of 1:1, adding 3mL of methanol into the round-bottom flask, heating and stirring the mixed powder and the methanol in a water bath at 50 ℃ for 2h, filtering, standing and volatilizing the filtrate for 4 days, and collecting a solid phase substance to obtain acetamiprid-oxalic acid eutectic and white crystal powder, wherein the test conditions are that the Cu-K α target tube voltage is 40kV, the tube current is 10mA, the scanning speed is 2 DEG/min and the PXRD diffraction pattern of the product is the same as that of example 1 by using an X-ray diffractometer of model D8 of BRUKER company Germany.
Example 3
The preparation method of the acetamiprid-oxalic acid eutectic crystal is implemented according to the following steps:
putting mixed powder of 0.222g of acetamiprid raw material medicine and 0.090g of oxalic acid into a round-bottom flask according to the molar ratio of 1:1, adding 10mL of ethanol into the round-bottom flask, heating and stirring the mixed powder and the ethanol in a water bath at 30 ℃ for 4 hours, filtering, standing and volatilizing the filtrate for 5 days, and collecting a solid phase substance to obtain acetamiprid-oxalic acid eutectic and white crystal powder, wherein the test conditions are that the Cu-K α target tube voltage is 40kV, the tube current is 10mA, the scanning speed is 2 DEG/min and the PXRD diffraction pattern of the product is the same as that of example 1 by using an X-ray diffractometer of model D8 of BRUKER company of Germany.
Example 4
The preparation method of the acetamiprid-acetic acid eutectic crystal is implemented according to the following steps:
putting mixed powder of 0.222g of acetamiprid raw material medicine and 0.060g of acetic acid into a round-bottom flask according to the molar ratio of 1:1, adding 10mL of ethanol into the round-bottom flask, heating and stirring the mixed powder and the ethanol in a water bath at 30 ℃ for 4 hours, filtering, standing and volatilizing filtrate for 4 days, and collecting a solid phase substance to obtain acetamiprid-acetic acid eutectic and white crystal powder, wherein the solid phase substance is measured by using a D8X-ray diffractometer of BRUKER company Germany under the test conditions of 40kV target tube voltage of Cu-K α target, 10mA tube current and 2 DEG/min scanning speed, and the PXRD diffraction pattern of the product is different from that of the acetamiprid raw material medicine and the acetic acid.
Example 5
And (3) determining the melting point of the acetamiprid-oxalic acid eutectic:
the melting point of the eutectic compound prepared in example 1 is 142.5 ℃ and the melting point of acetamiprid is 102 ℃ and the melting point of oxalic acid is 101 ℃ by using a Shanghai Jiahang WRS-1C type melting point tester, and compared with the simple substances of acetamiprid and oxalic acid, the melting points of the two substances in the eutectic are respectively increased by 40.5 ℃ and 41.5 ℃, so that the eutectic compound has a great promotion effect on the stability of the acetamiprid.
Example 6
Solubility test of acetamiprid-oxalic acid eutectic:
the dissolution rates of the acetamiprid-oxalic acid eutectic sample prepared in example 1 and the acetamiprid excess powder in a normal saline solution were respectively measured by the method of dissolution rate of excess powder. Respectively placing an excessive acetamiprid-oxalic acid eutectic sample and an acetamiprid sample with equal weight into 2 eggplant-shaped flasks with the volume of 100mL, placing the eggplant-shaped flasks into a water bath kettle, simultaneously adding 20mL of physiological saline solution, and starting timing, wherein the water bath temperature is 25 +/-0.5 ℃. The test lasted 180 minutes, and 0.5mL was sampled at 1, 2, 3, 4, 5, 10, 15, 30, 60, 120, 180 minutes, with the results shown in FIG. 3.
As can be seen from the figure, the maximum solubility 7430mg/L of the acetamiprid-oxalic acid eutectic in physiological saline is higher than 4230mg/L of acetamiprid, which shows that the pharmaceutical eutectic can improve the solubility of the acetamiprid, and research results provide scientific basis for improving the bioavailability of the acetamiprid and further exerting the insecticidal effect of the acetamiprid.
Example 7
Seed treatment test of acetamiprid-oxalic acid eutectic:
1) the preparation of the acetamiprid-oxalic acid eutectic-containing suspension seed coating agent comprises the following steps:
100g of acetamiprid-oxalic acid eutectic, 60g of sodium salt of naphthalene sulfonic acid formaldehyde polymer, 70g of sodium lauryl sulfate, 10g of silicone oil, 10g of sodium acrylate, 70g of glycerol and 20g of gelatin are added into 500g of water, and the mixture is supplemented to 1000g of deionized water, stirred uniformly, sheared at high speed, sanded by a wet method, homogenized and filtered to obtain the suspended seed coating agent.
2) Preparing a suspension seed coating agent containing acetamiprid and oxalic acid:
adding 71.2g of acetamiprid, 28.8g of oxalic acid, 60g of sodium salt of a naphthalene sulfonic acid formaldehyde polymer, 70g of sodium lauryl sulfate, 10g of silicone oil, 10g of sodium acrylate, 70g of glycerol and 20g of gelatin into 500g of water, supplementing 1000g of deionized water, uniformly stirring, performing high-speed shearing, performing wet sanding, and finally performing homogenization and filtration to obtain the suspension seed coating agent.
3) Preparing the acetamiprid-containing suspension seed coating agent:
adding 71.2g of acetamiprid, 60g of sodium salt of naphthalene sulfonic acid formaldehyde polymer, 70g of sodium lauryl sulfate, 10g of silicone oil, 10g of sodium acrylate, 70g of glycerol and 20g of gelatin into 500g of water, supplementing to 1000g of deionized water, uniformly stirring, then carrying out high-speed shearing, wet sanding, and finally carrying out homogeneous filtration to obtain the suspended seed coating agent.
4) Seed treatment test:
1kg of corn seeds (Zhengdan 958, commercially available from scientific and technological Co., Ltd., Henan Qiu Happy variety) and 5g of the acetamiprid-oxalic acid eutectic-containing suspension seed coating agent are mixed uniformly, a control group 1 is provided in which 1kg of corn seeds and 5g of the acetamiprid-oxalic acid eutectic-containing suspension seed coating agent are mixed uniformly, a control group 2 is provided in which 1kg of corn seeds and 5g of the acetamiprid-containing suspension seed coating agent are mixed uniformly, a control group 3 is provided in which 1kg of corn seeds and 5g of clear water are mixed uniformly, and the treated seeds are all placed in a ventilation place to be dried. 100 treated seeds are respectively taken and sowed in a germination box, a germination test is carried out according to GB/T3543.5-1995, the germination rate is counted on the 3 rd day, and the test result is as follows: the germination rate of the acetamiprid-oxalic acid eutectic test group is 94%, the germination rate of the control 1 group is 81%, the germination rate of the control 2 group is 82%, and the germination rate of the control 3 group is 94%.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (10)
1. An acetamiprid cocrystal, comprising: acetamiprid (acetamiprid) and organic acids; wherein the molar ratio of the acetamiprid (acetamiprid) to the organic acid is 10: 1-1: 10.
2. A co-crystal according to claim 1, wherein the organic acid is a carboxylic acid; preferably any one of acetic acid, oxalic acid or malonic acid; oxalic acid is more preferred.
3. A co-crystal according to claim 1, wherein the molar ratio of acetamiprid to organic acid is 5:1 to 1: 5; the preferable molar ratio is 3: 1-1: 3; still more preferred is a molar ratio of 2:1 to 1: 2.
4. A co-crystal according to any of claims 1 to 3, comprising acetamiprid and oxalic acid, wherein the molar ratio of acetamiprid to oxalic acid is 1:1 to 1: 2; the preferred molar ratio is 1: 1.
5. Co-crystal according to claim 1, characterized in that at least 4 of the following diffraction peaks, given in 2 Θ values, are shown in the spectrum: 7.591 degree plus or minus 0.2, 11.386 degree plus or minus 0.2, 12.834 degree plus or minus 0.2, 13.202 degree plus or minus 0.2, 15.120 degree plus or minus 0.2, 18.180 degree plus or minus 0.2, 19.181 degree plus or minus 0.2, 19.998 degree plus or minus 0.2, 20.955 degree plus or minus 0.2, 21.915 degree plus or minus 0.2, 22.670 degree plus or minus 0.2, 23.752 degree plus or minus 0.2, 24.731 degree plus or minus 0.2, 26.284 degree plus or minus 0.2, 27.404 degree plus or minus 0.2, 27.729 degree plus or minus 0.2 and 30.444 degree plus or minus 0.2.
6. The method of claim 1, wherein the acetamiprid is mixed with an organic acid, an alcohol solvent is added, the mixture is stirred with or without heating and then filtered, and the filtrate is left to stand to collect a solid as the cocrystal.
7. The production method according to claim 6, wherein the organic acid is a carboxylic acid; preferably any one of acetic acid, oxalic acid or malonic acid; oxalic acid or malonic acid is further preferable; oxalic acid is further preferable;
the heating condition is heating at 30-50 ℃;
the alcohol solvent is any one or a mixture of methanol, ethanol, propanol or butanol; preferably methanol or ethanol;
the solid-liquid ratio of the mixture of the acetamiprid and the organic acid to the alcohol solvent is (0.3-0.4) g, (3-4) mL; preferably (0.311-0.313) g (3-4) mL.
8. An agricultural formulation comprising an effective amount of an acetamiprid cocrystal according to any one of claims 1 to 5; preferably, the composition also comprises an agriculturally acceptable preparation carrier or a preparation auxiliary agent.
9. A method for controlling pests, which comprises applying a pesticidally effective amount of the acetamiprid cocrystal according to any one of claims 1 to 5 or the agricultural formulation according to claim 8 to the pests and/or their habitat.
10. Use of an acetamiprid cocrystal according to any one of claims 1 to 5 or an agricultural formulation according to claim 8 for controlling pests.
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| CN113861105A (en) * | 2021-11-08 | 2021-12-31 | 海利尔药业集团股份有限公司 | Co-crystal of acetamiprid and organic acid, preparation method and application thereof |
| CN113999181A (en) * | 2021-12-08 | 2022-02-01 | 海利尔药业集团股份有限公司 | Eutectic crystal of tebuconazole and organic acid and preparation method and application thereof |
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