CN115636943B - Acetoxy (2-aminobenzimidazole) -zinc complex and preparation method and application thereof - Google Patents
Acetoxy (2-aminobenzimidazole) -zinc complex and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of nitrogen-containing heterocyclic metal coordination compounds, in particular to an acetoxy (2-aminobenzimidazole) -zinc complex, a preparation method and application thereof. The invention provides a compound acetoxy (2-aminobenzimidazole) -zinc complex, which has an inhibiting effect on gray mold, powdery mildew, angular leaf spot, soft rot and ulcer and has a wide application prospect in the field of pesticides; meanwhile, the invention also provides a preparation method for synthesizing the target compound acetoxy (2-aminobenzimidazole) -zinc complex through the hydrothermal reaction of the methyl-1H-benzimidazole-2-yl carbamate compound and the zinc salt, so that the precipitation and crystallization effects of the product are effectively improved. The invention provides a green and environment-friendly method for synthesizing the high-purity heterocyclic metal coordination compound with bactericidal activity in high yield, which is suitable for industrial mass production and has wide application prospect and higher economic benefit.
Description
Technical Field
The invention relates to the technical field of nitrogen-containing heterocyclic metal coordination compounds or pesticide bactericides, in particular to an acetoxy (2-aminobenzimidazole) -zinc complex, a preparation method and application thereof.
Background
Pesticides have important significance for agricultural development, and a large number of synthetic pesticides are being introduced for improving crop yield. However, the irrational application leads to the rising of the drug resistance of pests and the increasing of pollution to an ecological system, and in order to adapt to the national policy and industry development trend, the design of introducing metal ions with sterilization efficacy into molecules with sterilization activity, and developing novel pesticide molecules with sterilization efficacy by forming a mode of structurally stable metal heterocyclic complexes has important significance for developing novel green pesticides with safety, high efficiency and economy.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides an acetoxyl (2-aminobenzimidazole) -zinc complex, and a preparation method and application thereof. The method is an environment-friendly method, and can synthesize the heterocyclic metal coordination compound with novel structure and excellent bactericidal activity, wherein the purity and the yield of the heterocyclic metal coordination compound are high.
In order to achieve the above object, the present invention provides the following.
The invention provides an acetoxy (2-aminobenzimidazole) -zinc complex with a chemical formula of [ C ] 18 H 18 N 6 O 4 Zn 2 ] n The structural formula is as follows:
preferably, the X-ray powder-phase-match pattern 2 theta diffraction angle of the acetoxy (2-amino benzimidazole) -zinc complex has characteristic diffraction peaks at 8.5, 12.2, 17.5, 22.1 and 24.9.
The invention also provides a preparation method of the acetoxy (2-aminobenzimidazole) -zinc complex, which is to carry out hydrothermal reaction on the methyl-1H-benzimidazole-2-yl carbamate compound and zinc salt to obtain the target product acetoxy (2-aminobenzimidazole) -zinc complex.
Preferably, the preparation method specifically comprises the following steps:
(1) Adding a methyl-1H-benzimidazole-2-yl carbamate compound into a solvent, and adding zinc salt into the solvent to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to a specified temperature by programming, and reacting for a period of time at constant temperature;
(3) And (3) performing constant-temperature reaction on the reactant obtained in the step (2) for a certain time, and performing programmed cooling to room temperature to obtain the target product of the acetoxy (2-aminobenzimidazole) -zinc complex.
Preferably, the zinc salt in the step (1) is at least one of zinc acetate, zinc sulfate, zinc phosphate, zinc chloride or a corresponding water crystallization compound; more preferred is zinc acetate dihydrate.
Preferably, the molar ratio of methyl-1H-benzimidazol-2-ylcarbamate to zinc salt in step (1) is 1-4:1, wherein the number of moles of zinc salt is calculated as zinc element. More preferably 2:1.
Preferably, the solvent in the step (1) is water, including at least one of purified water, deionized water and distilled water.
Preferably, the volume of the solvent in the step (1) is 21.4-100L/mol based on the amount of zinc salt.
Preferably, the programmed temperature rise in the step (2) is set to a rate of 2-10 ℃/min from room temperature to the specified temperature. By adopting the technical scheme, the temperature rising rate can be controlled, so that the target compound with high purity and high yield is further obtained.
Preferably, the specified temperature of the isothermal reaction stage in step (2) is 120-150 ℃, more preferably 140 ℃. At this temperature, the reaction rate can be further increased, and the target compound with high purity and high yield can be further obtained.
Preferably, the isothermal reaction time in step (2) is 100-150 hours, more preferably 120 hours. The target product with high purity and high yield can be further obtained under the reaction time, and the reaction energy consumption and the like are further reduced on the premise of ensuring the completion of the reaction.
Preferably, in the step (2), the mixed solution obtained in the step (1) is filled into a polytetrafluoroethylene lining reaction kettle, the filled reaction kettle is placed into an oven, the temperature programming is set to reach the specified temperature, and the reaction is carried out for a period of time at constant temperature.
Preferably, the program cooling in the step (3) is set to be 1-5 ℃/h from the appointed temperature to the room temperature. By adopting the technical scheme, the cooling rate can be controlled, which is favorable for powder crystal development, so that the target product with high purity can be better obtained, and meanwhile, the yield is high.
Preferably, the reaction system in the step (3) further comprises a post-treatment after being cooled to room temperature, wherein the post-treatment is a conventional post-treatment step, including filtration and drying, more preferably filtration is a conventional filtration, including normal pressure filtration and reduced pressure filtration, drying is a conventional drying, more preferably drying is oven drying, and the temperature is 100-120 ℃, more preferably 105 ℃. The target product can be further purified by the post-treatment step to obtain the target product with high purity, but the post-treatment step disclosed by the invention is only one of the conventional post-treatment steps, but the post-treatment step is not limited to the post-treatment step disclosed by the invention, and any conventional post-treatment step which can be used for improving the purity of the target product is an operation step which can be considered by adopting the technical scheme disclosed by the invention.
Preferably, the room temperature of the invention is 0-40 ℃.
The invention also provides an application of the acetoxy (2-aminobenzimidazole) -zinc complex or the acetoxy (2-aminobenzimidazole) -zinc complex prepared by the preparation method, mainly an application in preparing antibacterial/bacteriostatic/sterilizing medicines, and more preferably an application in preparing agricultural antibacterial/bacteriostatic/sterilizing medicines; the application is that the acetoxy (2-aminobenzimidazole) -zinc complex is used as one of main antibacterial active substances or the only antibacterial active substance is applied to the preparation of antibacterial/bacteriostatic/sterilizing medicines; more preferably, the acetoxy (2-aminobenzimidazole) -zinc complex is used as one of main antibacterial active substances or the only antibacterial active substance of the pesticide; more preferably, the bacteria aimed by the antibacterial/bacteriostatic/bactericidal medicine is at least one of bacteria causing gray mold, powdery mildew, angular leaf spot, canker and soft rot; more preferably, the pesticide is used for at least one of gray mold, powdery mildew, angular leaf spot, ulcer and soft rot.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a novel compound acetoxy (2-aminobenzimidazole) -zinc complex, which has an inhibiting effect on gray mold, powdery mildew, angular leaf spot, ulcer and soft rot, and particularly has an excellent inhibiting effect on the inhibiting effect on angular leaf spot, ulcer and soft rot, so that the compound has a wide application prospect in the pesticide field; meanwhile, the invention also provides a preparation method of the novel compound acetoxy (2-aminobenzimidazole) -zinc complex, the purity of the product obtained by the preparation method provided by the invention reaches 99.9%, the yield reaches 64%, and the preparation method for preparing the high-purity compound with high yield is provided for the compound for the first time; meanwhile, the preparation method takes water as a solvent, and the complex is synthesized by a hydrothermal method, so that the precipitation and crystallization effects of the product are effectively improved; the preparation method is simple and convenient, has concise and environment-friendly operation steps, is an environment-friendly method for synthesizing the high-purity heterocyclic metal coordination compound with bactericidal activity in high yield, is suitable for industrial mass production, and has wide application prospect and higher economic benefit.
Drawings
FIG. 1 is a comparative graph of X-ray powder diffraction pattern (upper) and single crystal diffraction data simulated graph (lower) of acetoxy (2-aminobenzimidazole) -zinc complex prepared according to example 1 of the present invention;
FIG. 2 is an infrared spectrum of an acetoxy (2-aminobenzimidazole) -zinc complex prepared in example 1 of the present invention;
FIG. 3 is a view showing the structure of an X-ray single crystal of the acetoxy (2-aminobenzimidazole) -zinc complex prepared in example 1 according to the present invention.
Detailed Description
The technical scheme of the invention is further specifically described below through specific embodiments and with reference to the accompanying drawings. In the specific embodiment of the invention, the room temperature is preferably 20-35 ℃.
Example 1
133.8mg (0.70 mmol) of methyl-1H-benzimidazol-2-ylcarbamate (carbendazim) were added to 10mL of purified water, 76.8mg (0.35 mmol) of zinc acetate dihydrate were added to the above solution, and then the solution was charged into a reaction vessel containing a polytetrafluoroethylene liner having a volume of 25mL, and the reaction vessel was put into an oven, and was first allowed to react at a constant temperature of 2℃per minute from room temperature to 140℃and then at 140℃for 120 hours, and then allowed to cool at a rate of 2℃per hour from 140℃to room temperature, which in this example was about 30℃in summer. After the reaction liquid is cooled to room temperature, the reaction kettle is opened, the lining is taken out, the lining of the reaction kettle is washed by purified water, the filtration is carried out at normal pressure, and the solid is naturally dried, or the solid can be dried at 100-120 ℃, especially about 105 ℃. The target product of the acetoxy (2-aminobenzimidazole) -zinc complex is obtained, the yield is 64 percent, and the purity is 99.9 percent.
The X-ray powder diffraction pattern of the acetoxy (2-aminobenzimidazole) -zinc complex of the compound prepared in the embodiment is shown in figure 1, characteristic diffraction peaks are arranged at 2 theta diffraction angles=8.5, 12.2, 17.5, 22.1 and 24.9, the X-ray powder diffraction pattern of the crystal simulation is consistent with the actually measured powder X-ray diffraction pattern, the infrared spectrogram is shown in figure 2, and the X-ray single crystal structure is shown in figure 3. The chemical formula of the compound is [ C 18 H 18 N 6 O 4 Zn 2 ] n N is more than or equal to 1, and the structural formula of the compound is shown as follows:
the crystallographic data of the acetoxy (2-aminobenzimidazole) -zinc complex prepared in this example are shown in Table 1.
TABLE 1 Crystal data table of acetoxy (2-aminobenzimidazole) -zinc complex
Example 2
133.8mg (0.70 mmol) of methyl-1H-benzimidazol-2-ylcarbamate (carbendazim) are added to 10mL of purified water, 56.5mg (0.35 mmol) of zinc sulfate are added to the above solution, the solution is then charged into a reaction vessel containing a polytetrafluoroethylene liner having a volume of 25mL, the reaction vessel is put into an oven, the reaction vessel is first allowed to react at a constant temperature of 140℃from room temperature to 140℃at a rate of 2℃per minute for 120 hours at 140℃and then allowed to cool from 140℃to room temperature at a rate of 2℃per hour. After the reaction solution is cooled to room temperature, opening the reaction kettle, taking out the lining, flushing the lining of the reaction kettle with purified water, filtering at normal pressure, and naturally airing to obtain the target product of the acetoxy (2-aminobenzimidazole) -zinc complex, wherein the yield is 45%, and the purity is 99.9%.
Example 3
66.9mg (0.35 mmol) of methyl-1H-benzimidazol-2-ylcarbamate (carbendazim) was added to 10mL of purified water, 76.8mg (0.35 mmol) of zinc acetate dihydrate was added to the above solution, followed by loading into a reaction vessel containing a polytetrafluoroethylene liner having a volume of 25mL, placing the reaction vessel into an oven, first raising the temperature from room temperature to 140℃at a rate of 2℃per minute, then reacting at a constant temperature of 140℃for 120 hours, and then lowering the temperature from 140℃to room temperature at a rate of 2℃per hour. After the reaction solution is cooled to room temperature, opening the reaction kettle, taking out the lining, flushing the lining of the reaction kettle with purified water, filtering at normal pressure, and naturally airing to obtain the target product of acetoxy (2-aminobenzimidazole) -zinc, wherein the yield is 50%, and the purity is 99.9%.
Example 4
267.6mg (1.40 mmol) of methyl-1H-benzimidazol-2-ylcarbamate (carbendazim) was added to 10mL of purified water, 76.8mg (0.35 mmol) of zinc acetate dihydrate was added to the above solution, followed by loading into a reaction vessel containing a polytetrafluoroethylene liner having a volume of 25mL, placing the reaction vessel into an oven, first raising the temperature from room temperature to 140℃at a rate of 2℃per minute, then reacting at a constant temperature of 140℃for 120 hours, and then lowering the temperature from 140℃to room temperature at a rate of 2℃per hour. After the reaction solution is cooled to room temperature, opening the reaction kettle, taking out the lining, flushing the lining of the reaction kettle with purified water, filtering at normal pressure, and naturally airing to obtain the target product of acetoxy (2-aminobenzimidazole) -zinc, wherein the yield is 48%, and the purity is 99.9%.
Example 5
133.8mg (0.70 mmol) of methyl-1H-benzimidazol-2-ylcarbamate (carbendazim) are added to 7.5mL of purified water, 76.8mg (0.35 mmol) of zinc acetate dihydrate are added to the above solution, the solution is then charged into a reaction vessel containing a polytetrafluoroethylene liner having a volume of 25mL, the reaction vessel is placed into an oven, the reaction vessel is first allowed to stand at a constant temperature of 140℃from room temperature to 140℃at a rate of 2℃per minute, and then allowed to stand at a constant temperature of 140℃for 120 hours, and then allowed to stand at a rate of 2℃per hour from 140℃to room temperature. After the reaction solution is cooled to room temperature, opening the reaction kettle, taking out the lining, flushing the lining of the reaction kettle with purified water, filtering at normal pressure, and naturally airing to obtain the target product of acetoxy (2-aminobenzimidazole) -zinc, wherein the yield is 52% and the purity is 99.9%.
Example 6
133.8mg (0.70 mmol) of methyl-1H-benzimidazol-2-ylcarbamate (carbendazim) are added to 20mL of purified water, 76.8mg (0.35 mmol) of zinc acetate dihydrate are added to the above solution, the solution is then charged into a reaction vessel containing a polytetrafluoroethylene liner having a volume of 25mL, the reaction vessel is placed into an oven, the reaction vessel is first allowed to react at a constant temperature of 140℃from room temperature to 140℃at a rate of 2℃per minute for 120 hours, and then allowed to cool from 140℃to room temperature at a rate of 2℃per hour. After the reaction solution is cooled to room temperature, opening the reaction kettle, taking out the lining, flushing the lining of the reaction kettle with purified water, filtering at normal pressure, and naturally airing to obtain the target product of acetoxy (2-aminobenzimidazole) -zinc, wherein the yield is 53% and the purity is 99.9%.
Example 7
The preparation was the same as in example 1, except that the temperature programming was set to rise from room temperature to the specified temperature at a rate of 10 ℃/min, 42% yield and 87% purity.
Example 8
The preparation was carried out as in example 1, except that the temperature at which the reaction stage was carried out was 120℃and the yield was 57% and the purity was 82%.
Example 9
The preparation was carried out as in example 1, except that the temperature at which the reaction stage was carried out was set at 150℃and the yield was 52% and the purity was 79%.
Example 10
The preparation method is the same as in example 1, except that the programmed cooling is set at a rate of 1 ℃/h from the specified temperature to room temperature. The yield was 54% and the purity was 86%.
Example 11
The preparation method is the same as in example 1, except that the programmed cooling is set at a rate of 5 ℃/h from the specified temperature to room temperature. The yield was 49% and the purity was 72%.
Example 12
The product of the above example 1, acetoxy (2-aminobenzimidazole) -zinc complex (compound No. CHH-08), was subjected to an indoor bioactivity test, which was performed by the company limited of the chemical industry institute of Zhejiang province, and the specific experimental contents are as follows:
(1) The purpose of the experiment is as follows: the indoor bacteriostatic effect of compound CHH-08 (1) was evaluated.
(2) Test target: bacterial sources such as powdery mildew, rust disease, banded sclerotial blight, gray mold, bacterial angular leaf spot, ulcer disease, soft rot and the like are cultured for a long time by a test company laboratory.
(3) Test treatment: compound CHH-08 (1) was formulated in DMF for 1% use. The antibacterial effect of the compounds on the test targets at the dosage of 200mg/L is evaluated by adopting a living potting method; the antibacterial effect of these compounds on the test targets at a dose of 50mg/L was evaluated by an ex vivo method.
(4) The test method comprises the following steps: taking cucumber seedlings in a one-leaf period as cucumber powdery mildew and cucumber gray mold test materials, and taking corn seedlings in a three-leaf period as rust disease and sheath blight test materials. Spraying compound with concentration of 200mg/L in a fume hood, repeating for 2 times, replacing the test agent each time, cleaning the spraying device with tap water containing Tween 80, and naturally air-drying the agent-treated test material at room temperature. Inoculating sporangium suspension (the sporangium concentration is 2×105/ml) on cucumber leaves and corn leaves by adopting a spray type inoculator, inoculating 2ml of inoculated test materials into a greenhouse after each treatment, and culturing at room temperature; bacterial cakes (phi 5 mm) are inoculated on the front surfaces of corn leaves and cucumber leaves respectively for sheath blight and gray mold, the inoculated experimental materials are transferred into a climatic chamber for moisture preservation (humidity is more than 95 percent) and are cultured at the temperature of about 24 ℃, and after the blank control experimental materials are fully distributed with diseases, the results of the treatment experimental materials are investigated. SOP (bactericide coil) was evaluated with reference to the biological activity of the created pesticide. The results of the product obtained in example 1 on a common screen of fungal test targets are shown in Table 2.
The results of the product obtained in example 1 on a common screen of bacterial test targets are shown in Table 3.
Table 2 product general screening results for fungal test targets
Table 3 results of product screening for bacterial test targets
(5) Results: as can be seen from the data in tables 2 and 3, CHH-08, 1 compound, showed no significant activity but some activity against gray mold and powdery mildew when subjected to common screening of selected test targets at a concentration of 200 mg/L; but the test targets are screened at the concentration of 50mg/L, the CHH-08 has 100 percent of inhibiting effect on angular leaf spot and ulcer, has 85 percent of inhibiting effect on soft rot and shows excellent antibacterial activity.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the invention in any way, but other variations and modifications are possible without exceeding the technical solutions described in the claims.
Claims (10)
1. An acetoxy (2-aminobenzimidazole) -zinc complex, which is characterized in that the chemical formula is [ C ] 18 H 18 N 6 O 4 Zn 2 ] n Crystallographic data and parameters with the following characteristics:
。
2. A process for the preparation of an acetoxy (2-aminobenzimidazole) -zinc complex according to claim 1, characterized in that the process is a hydrothermal reaction of a methyl-1H-benzimidazol-2-ylcarbamate compound with a zinc salt to obtain the acetoxy (2-aminobenzimidazole) -zinc complex.
3. A process for the preparation of an acetoxy (2-aminobenzimidazole) -zinc complex according to claim 2, characterized in that the process comprises the steps of:
(1) Adding a methyl-1H-benzimidazole-2-yl carbamate compound into a solvent, and adding zinc salt to obtain a mixed solution;
(2) The mixed solution is programmed to be heated to a specified temperature and reacts at a constant temperature;
(3) And (3) performing constant temperature reaction for a certain time, and then performing program cooling to room temperature to obtain the acetoxy (2-aminobenzimidazole) -zinc complex.
4. A process for the preparation of an acetoxy (2-aminobenzimidazole) -zinc complex according to claim 3, characterized in that the zinc salt is at least one of zinc acetate and the corresponding water-crystallising compound.
5. A process for the preparation of an acetoxy (2-aminobenzimidazole) -zinc complex according to claim 3, characterized in that in step (1) the molar ratio of methyl-1H-benzimidazol-2-ylcarbamate to zinc salt is 1-4:1.
6. A process for the preparation of an acetoxy (2-aminobenzimidazole) -zinc complex according to claim 3, wherein the solvent in step (1) is water.
7. A process for the preparation of an acetoxy (2-aminobenzimidazole) -zinc complex according to claim 3, characterized in that the programmed temperature rise in step (2) is set to a rate of 2-10 ℃/min from room temperature to the specified temperature.
8. The process for preparing an acetoxy (2-aminobenzimidazole) -zinc complex according to claim 3, wherein the constant temperature reaction stage in the step (2) has a designated temperature of 120 to 150 ℃ and a reaction time of 100 to 150 hours.
9. A process for the preparation of an acetoxy (2-aminobenzimidazole) -zinc complex according to claim 3, wherein the programmed cooling in step (3) is set at a rate of 1-5 ℃/h from the specified temperature to room temperature.
10. Use of an acetoxy (2-aminobenzimidazole) -zinc complex according to claim 1 or an acetoxy (2-aminobenzimidazole) -zinc complex obtained by the preparation method according to any one of claims 2 to 9 in the preparation of an antibacterial, bacteriostatic or bactericidal medicament.
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| CN101742915A (en) * | 2007-05-18 | 2010-06-16 | 爱今科技有限公司 | Bioactive acid agrichemical compositions and use thereof |
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