CN111187204B - 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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- CN111187204B CN111187204B CN202010029719.3A CN202010029719A CN111187204B CN 111187204 B CN111187204 B CN 111187204B CN 202010029719 A CN202010029719 A CN 202010029719A CN 111187204 B CN111187204 B CN 111187204B
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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
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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; 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 and form cocrystals with acetamiprid, and 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 bonds 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 conductivity activity and contact killing and stomach toxicity, is used for preventing and treating hemiptera (particularly aphids), thysanoptera and lepidoptera pests, is suitable for wide range of 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 pH9 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 acetamiprid has poor water solubility which is only 4250mg/L (25 ℃), and the phenomenon of austenite ripening is easy to occur in the storage process (especially above 35 ℃) of the acetamiprid preparation, especially the aqueous suspension agent, and the sedimentation phenomenon of effective components can occur with the lapse of time, even the final service performance can be influenced. 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 crystalline complexes of 4-hydroxybenzoic acid and a selected pesticide in patent application No. CN201080050233.2 and specifically disclosed crystalline complexes 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 has 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 show an increase in germination rate of 8%. The patent application with the application number of CN200810116936.5 of Jiangsuchun group Limited discloses an organic salt obtained by combining salicylic acid with pymetrozine or acetamiprid, but only discloses the safety and the 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 is combined with carboxylic acid such as oxalic acid and malonic acid to prepare the acetamiprid eutectic, so that the physicochemical properties of the acetamiprid can be effectively improved, the water solubility and the melting point of the acetamiprid can be improved, the stability and the processability of the acetamiprid can be enhanced, and a foundation is laid for further development and application of the acetamiprid.
Disclosure of Invention
The invention aims to overcome the inconvenience caused by the low water solubility and melting point of 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;
further, the organic acid is a carboxylic acid; preferably any one of acetic acid, oxalic acid or malonic acid; oxalic acid is preferred;
further, the molar ratio of the acetamiprid to the organic acid is 5; the preferred molar ratio is 3; the more preferable molar ratio is 2;
further, the pesticide comprises acetamiprid (acetamiprid) and oxalic acid, wherein the molar ratio of the acetamiprid (acetamiprid) to the oxalic acid is 1-1; the preferred molar ratio is 1;
further, the acetamiprid (acetamiprid) comprises acetamiprid technical product, single crystal form of acetamiprid, mixture of different crystal forms of acetamiprid, amorphous acetamiprid, acetamiprid solvate or mixture of amorphous acetamiprid and crystal form;
further, at least 4 of the following diffraction peaks given as 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 +/-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 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.
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 the solid as the cocrystal;
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 preparation, which comprises an effective amount of the acetamiprid cocrystal; 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 characteristics 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 crystal and excessive powder of 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:
placing mixed powder of 2.226g of acetamiprid bulk drug and 0.900g of oxalic acid into a round-bottom flask according to the mol ratio of 1. The test is carried out by using a D8 type X-ray diffractometer of BRUKER company in Germany, the test conditions are that the Cu-Kalpha 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 shown in figure 1.
The PXRD characteristic diffraction peaks 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, compared with PXRD of acetamiprid bulk drug and oxalic acid bulk drug, the obtained acetamiprid-oxalic acid cocrystal 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 bulk drug and 0.090g of oxalic acid into a round-bottom flask according to the mol ratio of 1. The test was carried out using an X-ray diffractometer model D8 from BRUKER, germany under the conditions of a Cu-K.alpha.target tube voltage of 40kV, a tube current of 10mA and a scanning speed of 2 DEG/min, and the PXRD diffraction pattern of the product was the same as that of example 1.
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 bulk drug and 0.090g of oxalic acid into a round-bottom flask according to the mol ratio of 1. The test was carried out using an X-ray diffractometer model D8 from BRUKER, germany, under the test conditions of Cu-Ka target tube voltage 40kV, tube current 10mA, scanning speed 2 °/min, and PXRD diffraction pattern of the product was the same as that of example 1.
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 mol ratio of 1. The test is carried out by using a D8 type X-ray diffractometer of BRUKER company in Germany, the test conditions are that the voltage of a Cu-K alpha target tube is 40kV, the tube current is 10mA, and the scanning speed is 2 DEG/min, and the PXRD diffraction pattern of the product is different from that of acetamiprid bulk drug and 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 excessive acetamiprid sample in 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 of the acetamiprid-oxalic acid eutectic in physiological saline is 7430mg/L higher than 4230mg/L of acetamiprid, which shows that the pharmaceutical cocrystal provided by the invention can improve the solubility of acetamiprid, and research results provide scientific basis for improving the bioavailability of acetamiprid and further exerting the insecticidal effect of 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) The preparation of the acetamiprid-and-oxalic acid-containing suspension seed coating agent comprises the following steps:
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 science and technology limited of the south Henan Qiu Happy variety) and 5g of the above suspension seed coating agent containing acetamiprid-oxalic acid eutectic are mixed uniformly, a control group 1 is provided in which 1kg of corn seeds and 5g of the above suspension seed coating agent containing acetamiprid and oxalic acid are mixed uniformly, a control group 2 is provided in which 1kg of corn seeds and 5g of suspension seed coating agent containing acetamiprid 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 (8)
1. An acetamiprid cocrystal, wherein the cocrystal consists of acetamiprid and oxalic acid, wherein the molar ratio of acetamiprid to oxalic acid is 1, and the following diffraction peaks, given as 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.
2. The method for preparing the co-crystal according to claim 1, wherein acetamiprid and oxalic acid are mixed, the molar ratio of the acetamiprid to the oxalic acid is 1.
3. The method according to claim 2, wherein the heating condition is heating at 30 to 50 ℃;
the solid-to-liquid ratio of the mixture of the acetamiprid and the oxalic acid to the methanol or the ethanol is (0.3-0.4) g, (3-4) mL.
4. The preparation method according to claim 3, wherein the solid-to-liquid ratio of the mixture of acetamiprid and oxalic acid to methanol or ethanol is (0.311 to 0.313) g (3 to 4) mL.
5. An agricultural formulation comprising an effective amount of the acetamiprid cocrystal of claim 1.
6. The agricultural formulation of claim 5, further comprising an agriculturally acceptable formulation carrier or formulation adjuvant.
7. A method for controlling pests, which comprises applying a pesticidally effective amount of the acetamiprid cocrystal of claim 1 or the agricultural formulation of any one of claims 5 to 6 to the pests and/or their habitat.
8. Use of an acetamiprid cocrystal according to claim 1 or an agricultural formulation according to any one of claims 5 to 6 for controlling pests.
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