CN115211436B - Agricultural synergistic bactericide and application thereof - Google Patents
Agricultural synergistic bactericide and application thereof Download PDFInfo
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- CN115211436B CN115211436B CN202210777791.3A CN202210777791A CN115211436B CN 115211436 B CN115211436 B CN 115211436B CN 202210777791 A CN202210777791 A CN 202210777791A CN 115211436 B CN115211436 B CN 115211436B
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- A—HUMAN NECESSITIES
- 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
- A01N47/08—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 one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- A—HUMAN NECESSITIES
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
-
- A—HUMAN NECESSITIES
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- A—HUMAN NECESSITIES
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C337/06—Compounds containing any of the groups, e.g. thiosemicarbazides
- C07C337/08—Compounds containing any of the groups, e.g. thiosemicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. thiosemicarbazones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Abstract
The invention belongs to the technical field of pesticide campholothurian, and in particular relates to an agricultural synergistic bactericide, which is campholothurian or consists of campholothurian and a commercial bactericide, wherein the mol ratio of the campholothurian to the commercial bactericide is 1-55:55-99, and the bactericide is one of tricyclazole, hexaconazole, difenoconazole, kresoxim-methyl, azoxystrobin and thiophanate-methyl. The invention prepares the camphor thiosemicarbazone with high efficiency, and uses the camphor thiosemicarbazone as a synergistic bactericide or combines the camphor thiosemicarbazone with a commercial bactericide, thereby improving the use effect of the existing commercial bactericide and reducing the pesticide consumption; the in vitro antibacterial activity of the agricultural synergistic bactericide for plant fungal diseases is tested, and the research result shows that the campholothurian shows a certain antibacterial activity for plant fungal diseases (especially rhizoctonia solani), and has the property of being used as a novel pesticide precursor compound or a synergistic agent.
Description
Technical Field
The invention belongs to the technical field of pesticide camphorthiosemicarbazone, and particularly relates to an agricultural synergistic bactericide and application thereof.
Background
The method for preventing and controlling plant diseases mainly comprises agricultural prevention and control, biological prevention and control and chemical prevention and control. The chemical control method is a method for controlling plant diseases by using chemical agents, has the advantages of high efficiency, quick effect, convenient use, high economic benefit and the like, and is the most main method for controlling plant diseases at present. Classes of antimicrobial agents (representative antimicrobial agents) widely used for controlling plant diseases include: inorganic (mancozeb), antibiotics (validamycin), microorganisms (antagonizing bacteria bacillus subtilis and bacillus cereus), organic phosphorus (pyrithione, iprobenfos), sterol biosynthesis inhibitors (tridemorph, triazolone), benzimidazoles (carbendazim, benomyl, qingjun, etc.), triazoles (hexaconazole, propiconazole, difenoconazole, etc.), methoxy acrylic esters (pyraclostrobin), succinic acid dehydrogenase inhibitors (thifluzamide), and the like.
However, since recent decades have seen limited development speeds of novel antibacterial agents, mainstream antibacterial agents such as validamycin, propiconazole, pyraclostrobin, thiaflunomide, etc. have been used for a long time, resulting in plant diseases developing different degrees of resistance to them. For example: validamycin is one of the most successful biogenic antibacterial agents and has been used for over 50 years. The action mechanisms of validamycin are found to include: inhibiting the activity of germ trehalase, so that the trehalase cannot be decomposed into glucose; inhibiting inositol biosynthesis to affect phospholipid production; inhibit bacterial cellulose degrading enzyme and polygalacturonase, thereby reducing pathogenic bacteria pathogenicity. Propiconazole belongs to triazole antibacterial agents, is a sterol methylation inhibitor, and mainly interferes with the biosynthesis of fungus sterols to inhibit the synthesis of ergosterol; pyraclostrobin is a novel broad-spectrum methoxy acrylic antibacterial agent, and has effects of protecting, treating and blade permeation and conduction by inhibiting mitochondrial respiration and finally causing cell death; thifluzamide is a succinate dehydrogenase inhibitor that inhibits succinate dehydrogenase in the tricarboxylic acid cycle of bacteria, resulting in cell death, and all 3 antibacterial agents have been used cumulatively for 30 years or more. Researches show that due to long-term repeated use and the reasons of medicine unscientific use and the like, plant diseases gradually generate different degrees of drug resistance to antibiotics such as validamycin, propiconazole, pyraclostrobin, thifluzamide and the like. If no novel substitute antibacterial agent or antibacterial synergist is present, the pathogen resistance will further rise, directly leading to the decrease of the plant disease control effect, and a huge threat will be formed for the planting safety and economic output of crops. Therefore, further development of novel alternative antibacterial agents or antibacterial potentiators having unique mechanisms of action is urgent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an agricultural synergistic bactericide for solving the problems of reduced use effect and improved resistance of the existing commercial antibacterial agent and prolonging the service life of the existing commercial antibacterial agent, aiming at the problems of reduced resistance and reduced control effect of plant diseases caused by long-term use of the commercial antibacterial agent.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an agricultural synergistic bactericide is campholothurian or is composed of campholothurian and commercial bactericide.
Preferably, the mol ratio of the camphorthiosemicarbazone to the commercial bactericide is 1-50:50-99, and the bactericide is one of tricyclazole, hexaconazole, difenoconazole, kresoxim-methyl, azoxystrobin and thiophanate-methyl.
The invention also aims to overcome the defects of the preparation process of the camphorthiosemicarbazone in the prior art, and provides the preparation method of the camphorthiosemicarbazone, which has the advantages of low reaction cost, mild operation condition, low energy consumption, environmental friendliness, high raw material conversion rate and high finished product yield.
The preparation method of the camphor thiosemicarbazone comprises the following steps: taking camphor and thiosemicarbazide as raw materials to react to obtain a crude product, and recrystallizing to obtain a finished product of camphor thiosemicarbazone.
In order to further ensure that the reaction is rapid and the product yield is high, camphor, thiosemicarbazide and a catalyst are respectively added under the condition of existence of a micromolecular alcohol solvent, the mixture is continuously stirred and mixed uniformly, then the reaction system is regulated to a proper temperature, the reaction is carried out for a proper time, a crude product of the camphor thiosemicarbazone is obtained, and a finished product of the camphor thiosemicarbazone is obtained after recrystallization.
Preferably, the molar ratio between the camphor and the thiosemicarbazide is 1:0.5-2.
Preferably, the small molecule alcohol solvent is selected from one of methanol, ethanol and isopropanol, and more preferably isopropanol, wherein the molar volume ratio of the camphor to the small molecule alcohol solvent is 1moL to 2L.
Preferably, the catalyst is a solution of inorganic acid or a solution of small molecular organic acid, the inorganic acid is hydrochloric acid or sulfuric acid, the small molecular organic acid is selected from one of formic acid, acetic acid and citric acid, the concentration of the catalyst is 5-15% wt, and the molar volume ratio of the camphor to the small molecular alcohol solvent is 1 mol:0.1L.
Preferably, the suitable temperature is 10 ℃ to 35 ℃ and the suitable time is 2h to 6h.
Preferably, the solvent used in the recrystallization is selected from one of ethanol, an aqueous ethanol solution, and an ethanol petroleum ether mixed solution.
Based on one general inventive concept, another object of the present invention is to protect the application of the agricultural synergistic bactericide in controlling plant fungal diseases.
Compared with the prior art, the method has the advantages that the camphor thiosemicarbazone is efficiently prepared and used as a synergistic bactericide or combined with a commercial bactericide, so that the use effect of the conventional commercial bactericide is improved, and the pesticide dosage is reduced; the in vitro antibacterial activity of the agricultural synergistic bactericide for plant fungal diseases is tested, and the research result shows that the campholothurian shows a certain antibacterial activity for plant fungal diseases (especially Rhizoctonia solani), and has the property of being used as a novel pesticide precursor compound or a synergistic agent.
Drawings
FIG. 1 is a route diagram of the present invention for the synthesis of camphorthiosemicarbazone;
FIG. 2 is a graph showing the hydrogen spectrum of the synthesized camphorthiosemicarbazone according to the present invention;
FIG. 3 is a graph showing the carbon spectrum of the synthesized camphorthiosemicarbazone of the present invention;
FIG. 4 is an infrared signature of the synthetic camphorthiosemicarbazone of the present invention;
FIG. 5 is a nuclear magnetic characterization diagram of the synthetic camphorthiosemicarbazone of the present invention;
FIG. 6 effect of ZNSN content variation on antibacterial activity of ZNSN/hexaconazole formulations;
FIG. 7 effect of ZNSN content variation on antibacterial activity of ZNSN/tricyclazole complex;
FIG. 8 effect of ZNSN content variation on antibacterial activity of ZNSN/difenoconazole compound;
FIG. 9 effect of ZNSN content variation on antibacterial activity of ZNSN/kresoxim-methyl complex;
FIG. 10 effect of ZNSN content variation on antibacterial activity of ZNSN/azoxystrobin complex;
FIG. 11 effect of ZNSN content variation on antibacterial activity of ZNSN/thiophanate-methyl formulations.
Detailed Description
The invention will be further described with reference to specific embodiments for the purpose of making the objects, technical solutions and advantages of the invention more apparent, but the invention is not limited to these examples. It should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below. In the present invention, the equipment, raw materials, etc. used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The terms "comprising," "including," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
Specific embodiments of the present invention are described in detail below.
Examples
The preparation method of the camphorthiosemicarbazone in the embodiment comprises the following steps:
1.522g (10 mmol) of camphor, 0.910g (10 mmol) of thiosemicarbazide, 20mLIPA (isopropanol) and 1mL of 10% HCl are respectively added into a 50mL round bottom flask equipped with a magnetic stirrer, the reaction is stirred for 4 hours at room temperature and 25 ℃, the progress of the reaction is detected by TLC, and the developing agent is petroleum ether and ethyl acetate (V petroleum ether/V ethyl acetate=4.5:1);
after the reaction is completed, filtering to obtain solid powder, recrystallizing and purifying by ethanol, filtering again, flushing the filter cake by petroleum ether for 2-3 times, and drying to obtain a pure product.
The specific synthetic route is shown in FIG. 1, which adopts 1 H NMR、 13 C NMR, FT-IR, HRMS to characterize the structure of the compound.
The characterization data of the camphorthiosemicarbazone structure are as follows: white needle-like crystals, yield: 93.24%; m.p.196-200 ℃; FT-IR v (cm) -1 ):3423,3250,3163(N-H),1739,1664(C＝N),1304(C＝S)； 1 H NMR(400MHz,DMSO)δ9.82(s,1H),8.04(s,1H),7.41(s,1H),3.35(s,1H),2.02(d,J＝18.0Hz,1H),1.92(t,J＝4.3Hz,1H),1.78(ddd,J＝11.9,8.0,3.8Hz,1H),1.72–1.66(m,1H),1.30–1.25(m,1H),1.20–1.15(m,1H),0.95(s,2H),0.88(s,2H),0.69(s,2H). 13 C NMR(101MHz,DMSO-d 6 )δ178.57,166.64,52.87,47.99,43.80,35.00,32.82,27.20,19.69,18.95,11.61.HRMS:m/z 225.1378[M+H] + .
Test examples
1. The Rhizoctonia solani (Rhizoctonia solani) required for the test is provided and cultivated by the woody spice (Huadong) engineering technology research center of the forest and grass bureau of the university of agriculture in Jiangxi province.
2. Experimental procedure
2.1 preparation of Medium
Weighing a proper amount of potato dextrose agar medium (PDA), mixing the PDA and deionized distilled water, boiling for 30min, taking out, adding into a large-sized measuring cylinder to a certain volume (a proper measuring cylinder is selected according to the volume of liquid), pouring into a 100mL measuring cylinder to a certain volume of 60mL finally, pouring into a conical flask, and sealing by using a sealing film with a core and a rubber band. And finally, placing the conical flask and a pipette tip required for subsequent experiments into a vertical pressure steam sterilizing pot for sterilization.
2.2 preparation of medicated Flat plate
Preparing a centrifuge tube with a certain specification, calculating required medicines, weighing the medicines by a ten-thousandth balance, loading the medicines into the centrifuge tube, putting a pipetting gun, a sealing film, a puncher and a centrifuge tube which are prepared in advance into a sterile ultra-clean workbench in a sterile room, and after a series of safe standard operations such as glove wearing and mask wearing are finished, preparing a culture dish (respectively marking dates, names of strains and compound and proportion concentration of the names on the culture dish). Then the ultraviolet lamp is turned on to sterilize for 30min, the sterilizing chamber is left, data are recorded, whether the air pressure of the sterilizing pot is too high or not is regularly observed, if so, the air release valve is turned on, and the experimental safety is ensured. After 30min, the sterilization of the sterile room is completed, and at the same time, the sterilization pot also completes the sterilization of the culture medium and related instruments, the conical flask with the PDA and the pipette are taken out, returned to the sterilization room for carrying out safe standard operation again, and the next experiment is started. Taking 1000 mu mol/L of the first gradient as an example, absorbing 400 mu L of a dissolving agent (the dissolving agent is selected from non-toxic, common and low-cost 95% absolute ethyl alcohol) by a liquid-transferring gun, injecting the dissolving agent into a centrifuge tube, sufficiently shaking and uniformly shaking the dissolving agent to completely dissolve the dissolving agent, then absorbing 200 mu L of a solvent into a 60mL conical flask containing a culture medium, shaking and uniformly mixing the solution for later use, wherein the conical flask is a concentration gradient of 1000 mu mol/L of a compound, then absorbing 200 mu L of the dissolving agent into the centrifuge tube, shaking and uniformly shaking the solution, absorbing 200 mu L of the solvent into a 60mL conical flask containing the culture medium, and the conical flask is a concentration gradient of 500 mu mol/L of the compound, so as to push the solution. The 60mL conical flask containing the culture medium is poured into a culture dish uniformly, and bacteria inoculation is prepared after the flask is cooled. In the process of preparing the drug-containing flat plate, the blank control group is also added with the dissolving agent with the same dosage, so that experimental errors are avoided.
2.3 inoculation and cultivation
Evenly pouring 60mL culture medium into 3 culture dishes, punching (vertically falling) by using a 5mm puncher (sterilizing and burning before use) after the culture medium is solidified (about 30min, and after the culture medium turns from deep yellow to light yellow), inoculating a 5mm fungus cake to the central position of the culture dishes by using an inoculating needle (sterilizing and burning by using an alcohol lamp before use), sealing by using a sealing film after inoculation is finished, and marking. Placing the surface of the culture dish after inoculation, which contains the culture medium, upwards in a 28 ℃ incubator for culture, and finally cleaning the experiment sanitation and eliminating a series of potential safety hazards.
2.4 data measurement and calculation
And measuring data when the colony of the blank control group (CK) grows to be two thirds of the whole culture dish, measuring the diameter of the colony by using a crisscross method, averaging, and subtracting the diameter (0.5 cm) of the colony to obtain the diameter of a single colony. Then, calculating the measured data to obtain the bacteriostasis rate, wherein the calculation formula is as follows:
calculation of EC according to steps and requirements using SPSS software 50 Virulence regression equation and correlation coefficient R 2 . Theoretical EC of Complex 50 (EC assuming no synergistic antibacterial effect between the two components of the formulation) 50 Values), the calculation method is as follows, taking a compound of 5% ZNSN and 95% tricyclazole as an example (molar content), theoretical EC 50 EC value equal to 5% multiplied by ZNSN positive control 50 EC of the value plus 95% multiplied by the tricyclazole positive control 50 Values.
3. Results and discussion
Antibacterial activity data for camphorthiosemicarbazone, 6 commercial antibacterial agents, and a combination of camphorthiosemicarbazone and commercial antibacterial agent of example 1 are set forth in table 1 below. In Table 1, A represents hexaconazole, B represents tricyclazole, C represents difenoconazole, D represents kresoxim-methyl, E represents azoxystrobin, F represents thiophanate-methyl, ZNSN represents campholothurian. A1 represents ZNSN containing 5% (mole content) of ZNSN/hexaconazole compound; a2 represents ZNSN containing 10% (mole content) of ZNSN/hexaconazole compound, A3 represents ZNSN containing 15% (mole content) of ZNSN in ZNSN/hexaconazole compound, and so on.
TABLE 1 antibacterial Activity data for Camphorthiosemicarbazone and pesticide formulations
Note that: a represents hexaconazole, B represents tricyclazole, C represents difenoconazole, D represents kresoxim-methyl, E represents azoxystrobin, F represents thiophanate-methyl, A1 means a complex of ZNSN accounting for 5% and hexaconazole accounting for 95%, ZNSN accounting for 10% in A2, ZNSN accounting for 25% in A5, and so on. "-" indicates no test data.
3.1 synergistic antimicrobial analysis of Camphorthiosemicarbazone and hexaconazole
As can be seen from Table 1, EC of thiosemicarbazone/hexaconazole complex (A1-A5) against Rhizoctonia solani 50 The value is between 0.07 mu mol/L and 0.11 mu mol/L, shows high-efficiency antibacterial activity, and the EC thereof 50 EC values were lower than those of both camphorthiosemicarbazone and hexaconazole 50 The value shows that compared with the camphorthiosemicarbazone and hexaconazole, the camphorthiosemicarbazone/hexaconazole compound has stronger antibacterial activity to Rhizoctonia solani, and also proves that the camphorthiosemicarbazone and hexaconazole have good synergistic antibacterial effect. The effect of ZNSN content variation on the antimicrobial activity of ZNSN/hexaconazole formulations is shown in FIG. 6. From FIG. 6, it can be seen that experiment EC of camphorthiosemicarbazone/hexaconazole complex 50 The values are all lower than the theoretical EC obtained by calculating the camphor thiosemicarbazone/hexaconazole compound according to the component proportion 50 Values (i.e. EC when camphorthiosemicarbazone and hexaconazole do not act synergistically) 50 Calculated), which further indicates that there is a synergistic antimicrobial effect between camphorthiosemicarbazone and hexaconazole. The camphorthiosemicarbazone/hexaconazole compound A2 shows the strongest antibacterial activity and EC thereof 50 The value is 0.07 mu mol/L, which shows that when the mol content of the campholothuromide is 10%, the two components in the campholothuromide/hexaconazole compound can form the strongest synergistic antibacterial effect.
3.2 synergistic antimicrobial analysis of Camphorthiosemicarbazone and tricyclazole
As can be seen from Table 1, EC of thiosemicarbazone/tricyclazole complex B1-B5 against Rhizoctonia solani 50 The value is between 40.87 mu mol/L and 93.11 mu mol/L, shows a certain antibacterial activity and has EC 50 All have low valuesEC in tricyclazole 50 Values. Compared with camphor thiosemicarbazone, brain thiosemicarbazone/tricyclazole compound B4-B5 has stronger antibacterial activity on Rhizoctonia solani and EC thereof 50 EC with values lower than those of camphorthiosemicarbazone 50 The value shows that compared with the camphorthiosemicarbazone, the camphorthiosemicarbazone/tricyclazole compound B4-B5 has stronger antibacterial activity on Rhizoctonia solani. The above results demonstrate that there is a good synergistic antimicrobial effect between camphorthiosemicarbazone and tricyclazole. The effect of ZNSN content variation on the antimicrobial activity of ZNSN/tricyclazole complexes is shown in FIG. 7. From FIG. 7, it can be seen that experiment EC of camphorthiosemicarbazone/tricyclazole complex 50 Values are all below their theoretical EC 50 Values, further indicating that there is a synergistic antimicrobial effect between camphorthiosemicarbazone and tricyclazole. Camphorthiosemicarbazone/tricyclazole complex B5 exhibits the lowest EC 50 The value (40.87 mu mol/L) shows that when the molar content of the campholothuromide is 25%, the strongest synergistic antibacterial effect can be formed between the two components in the campholothuromide/tricyclazole compound.
3.3 synergistic antibacterial analysis of Camphorthiosemicarbazone and difenoconazole
As can be seen from Table 1, EC of thiosemicarbazone/difenoconazole compound C1-C5 against Rhizoctonia solani 50 The value is between 0.03 mu mol/L and 0.27 mu mol/L, the efficient antibacterial activity is reflected, and the EC of the thiosemicarbazone/difenoconazole compound C3-C5 is reflected 50 EC with lower value than difenoconazole 50 The values show that the thiosemicarbazone/difenoconazole compound C3-C5 has stronger antibacterial activity to the Rhizoctonia solani compared with difenoconazole, and the thiosemicarbazone/difenoconazole compound C1-C5 has stronger antibacterial activity to the Rhizoctonia solani compared with the thiosemicarbazone, so that the good synergistic antibacterial effect between the thiosemicarbazone and the difenoconazole can be proved. The effect of ZNSN content variation on the antibacterial activity of ZNSN/difenoconazole compound is shown in figure 8. From FIG. 8, it can be seen that experiment EC of camphorthiosemicarbazone/difenoconazole complex 50 Values are all below their theoretical EC 50 Values, which further indicate camphora shrinkageThere is a synergistic antibacterial effect between thiosemicarbazide and difenoconazole. C1 to C2 experiments in formulations EC 50 Values are in an ascending trend, EC of C3 to C5 50 The value gradually decreases, and the camphorthiosemicarbazone/difenoconazole compound C5 shows the lowest EC 50 The value (0.03 mu mol/L) shows that when the molar content of the campholothuromide is 25%, the two components in the campholothuromide/difenoconazole compound can form the strongest synergistic antibacterial effect, and the campholothuromide/difenoconazole compound has strong antibacterial activity and good market prospect.
3.4 synergistic antibacterial analysis of Camphorthiosemicarbazone and kresoxim-methyl
As can be seen from Table 1, EC of thiosemicarbazone/kresoxim-methyl compound D1-D5 against Rhizoctonia solani 50 The EC value of the campholothurian/ether fungus ester compound D1-D5 is between 6.21 mu mol/L and 8.65 mu mol/L, which shows a certain antibacterial activity 50 EC values higher than that of kresoxim-methyl 50 The value shows that the synergy of the camphorthiosemicarbazone on the antibacterial activity of the kresoxim-methyl is not obvious. The effect of ZNSN content variation on the antibacterial activity of ZNSN/kresoxim-methyl complex is shown in FIG. 9. As can be seen from FIG. 9, the experiment EC of the thiosemicarbazone/kresoxim-methyl complex D1-D2 50 Values above its theoretical EC 50 Value, compound D3-D5 experiment EC with increasing ZNSN proportion 50 Values below its theoretical EC 50 The value of the thiosemicarbazone has the antibacterial synergistic effect on the kresoxim-methyl, but the thiosemicarbazone is not obvious. Camphorthiosemicarbazone/kresoxim-methyl compound D1 shows the lowest EC 50 The value (6.21 mu mol/L) shows that when the mol content of the campholothurian is 5%, the strongest synergistic antibacterial effect can be formed between the two components in the campholothurian/kresoxim-methyl compound.
3.5 synergistic antimicrobial analysis of campholothurian and azoxystrobin
As can be seen from Table 1, EC of thiosemicarbazone/azoxystrobin complex E1-E5 against Rhizoctonia solani 50 The value is between 0.19 mu mol/L and 0.39 mu mol/L, shows high-efficiency antibacterial activity, and the EC of the campholothurian/azoxystrobin compound E3-E5 50 EC with a value lower than azoxystrobin 50 Values indicating camphorthiosemicarbazone/azoxystrobinThe ester compound E3-E5 has stronger antibacterial activity to Rhizoctonia solani compared with azoxystrobin, and the camphorthiosemicarbazone/azoxystrobin compound E1-E5 has stronger antibacterial activity to Rhizoctonia solani compared with camphorthiosemicarbazone, so that good synergistic antibacterial effect exists between the camphorthiosemicarbazone and azoxystrobin. The effect of ZNSN content variation on the antibacterial activity of ZNSN/azoxystrobin complex is shown in FIG. 10. As can be seen from FIG. 10, experiment EC of camphorthiosemicarbazone/azoxystrobin complex E1-E5 50 Values are all below their theoretical EC 50 Values, further indicating that there is a synergistic antimicrobial effect between camphorthiosemicarbazone and azoxystrobin. Camphorthiosemicarbazone/azoxystrobin complex E5 shows the lowest EC 50 The value (0.19 mu mol/L) shows that when the mol content of the campholothurian is 25%, the strongest synergistic antibacterial effect can be formed between the two components in the campholothurian/azoxystrobin compound.
3.6 synergistic antibacterial analysis of Camphorthiosemicarbazone and thiophanate-methyl
As can be seen from Table 1, the EC of thiosemicarbazone/thiophanate-methyl compound F1-F5 against Rhizoctonia solani 50 The value is between 10.90 mu mol/L and 18.01 mu mol/L, shows a certain antibacterial activity and has EC 50 EC values were lower than those of both camphorthiosemicarbazone and thiophanate-methyl 50 The value shows that compared with the thiosemicarbazone and thiophanate-methyl, the thiosemicarbazone/thiophanate-methyl compound has stronger antibacterial activity to the Rhizoctonia solani, and also proves that the thiosemicarbazone and thiophanate-methyl have good synergistic antibacterial effect. The effect of ZNSN content variation on the antimicrobial activity of ZNSN/thiophanate-methyl formulations is shown in FIG. 11. As can be seen from FIG. 11, the experiment EC of the thiosemicarbazone/thiophanate-methyl compound F1-F5 50 Values are all below their theoretical EC 50 Values, further indicating that there is a synergistic antimicrobial effect between camphorthiosemicarbazone and thiophanate-methyl. Camphorthiosemicarbazone/thiophanate-methyl compound F2 shows the lowest EC 50 The value (10.90 mu mol/L) shows that when the mol content of the campholothuromide is 10%, the campholothuromide/thiophanate-methyl compound can be formed between two componentsThe strongest synergistic antibacterial effect is achieved.
In the test example, rice sheath blight germ is taken as a test strain, and a hypha growth rate method is adopted to research the synergistic antibacterial activity between campholothurian and 6 commercial antibacterial agents, so that the campholothurian has good synergistic antibacterial effects with hexaconazole, tricyclazole, difenoconazole, azoxystrobin and thiophanate-methyl respectively.
The above embodiments are merely preferred embodiments of the present invention, and any simple modification, modification and substitution changes made to the above embodiments according to the technical substance of the present invention are all within the scope of the technical solution of the present invention.
Claims (11)
1. The agricultural synergistic bactericide is characterized by comprising camphorthiosemicarbazone and hexaconazole, wherein the molar ratio of the camphorthiosemicarbazone to the hexaconazole is 5-25:75-95.
2. The agricultural synergistic bactericide is characterized by comprising camphorthiosemicarbazone and tricyclazole, wherein the molar ratio of the camphorthiosemicarbazone to the tricyclazole is 20-25:75-80.
3. The agricultural synergistic bactericide is characterized by comprising camphorthiosemicarbazone and difenoconazole, wherein the molar ratio of the camphorthiosemicarbazone to the difenoconazole is 15-25:75-85.
4. The agricultural synergistic bactericide is characterized by comprising camphorthiosemicarbazone and azoxystrobin, wherein the molar ratio of the camphorthiosemicarbazone to the azoxystrobin is 15-25:75-85.
5. The agricultural synergistic bactericide is characterized by comprising camphorthiosemicarbazone or camphorthiosemicarbazone and thiophanate-methyl, wherein the molar ratio of the camphorthiosemicarbazone to the thiophanate-methyl is 5-25:75-95.
6. An agricultural synergistic bactericide according to any one of claims 1 to 5, characterized in that the preparation method of camphorthiosemicarbazone comprises the following steps: taking camphor and thiosemicarbazide as raw materials to react to obtain a crude product, and recrystallizing to obtain a finished product of camphor thiosemicarbazone.
7. The agricultural synergistic bactericide according to claim 6, wherein camphor, thiosemicarbazide and catalyst are respectively added in the presence of isopropanol, and are continuously stirred and mixed uniformly, then the reaction system is regulated and controlled to 10-35 ℃ for 2-6 h, the crude product of camphor thiosemicarbazone is obtained, and then the finished product of camphor thiosemicarbazone is obtained after recrystallization.
8. An agricultural synergistic bactericide as claimed in claim 6, characterised in that the molar ratio between camphor and thiosemicarbazide is 1:0.5-2.
9. The agricultural synergistic bactericide according to claim 7, wherein the catalyst is a solution of an inorganic acid or a solution of a small molecular organic acid, the inorganic acid is hydrochloric acid or sulfuric acid, the small molecular organic acid is selected from one of formic acid, acetic acid and citric acid, the concentration of the catalyst is 5-15% wt., and the molar volume ratio between camphor and isopropanol is 1 mol:0.1L.
10. The agricultural synergistic bactericide according to claim 6, wherein the solvent used for recrystallization is selected from one of ethanol and ethanol petroleum ether mixed solution.
11. Use of an agricultural synergistic fungicidal agent as claimed in any of claims 1 to 10 for the control of plant fungal diseases, which are sheath blight of rice.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102754662A (en) * | 2012-07-31 | 2012-10-31 | 潘登 | Fungicidal composition for controlling rice diseases |
| WO2014100166A1 (en) * | 2012-12-19 | 2014-06-26 | Dow Agrosciences Llc | Pesticidal compositions and processes related thereto |
| CN104351231A (en) * | 2014-10-11 | 2015-02-18 | 中国农业大学 | Application of 4-chlorocinnamaldehyde thiosemicarbazone in plant disease control |
| CN107163657A (en) * | 2017-06-01 | 2017-09-15 | 中山市丽莎涂料有限公司 | A kind of radiation-preventing composition and a kind of coating additive and radiation shielding coating |
| CN109054491A (en) * | 2018-10-25 | 2018-12-21 | 合肥永泰新型建材有限公司 | A kind of metope radiation protection putty new material and preparation method thereof |
| WO2022042605A1 (en) * | 2020-08-26 | 2022-03-03 | 山东省联合农药工业有限公司 | Bactericidal composition comprising pyrazole amide compound and triazole bactericide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2002361689A1 (en) * | 2002-01-04 | 2003-07-30 | University Of Dayton | Non-toxic corrosion protection pigments based on cobalt |
-
2022
- 2022-07-04 CN CN202210777791.3A patent/CN115211436B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102754662A (en) * | 2012-07-31 | 2012-10-31 | 潘登 | Fungicidal composition for controlling rice diseases |
| WO2014100166A1 (en) * | 2012-12-19 | 2014-06-26 | Dow Agrosciences Llc | Pesticidal compositions and processes related thereto |
| CN104351231A (en) * | 2014-10-11 | 2015-02-18 | 中国农业大学 | Application of 4-chlorocinnamaldehyde thiosemicarbazone in plant disease control |
| CN107163657A (en) * | 2017-06-01 | 2017-09-15 | 中山市丽莎涂料有限公司 | A kind of radiation-preventing composition and a kind of coating additive and radiation shielding coating |
| CN109054491A (en) * | 2018-10-25 | 2018-12-21 | 合肥永泰新型建材有限公司 | A kind of metope radiation protection putty new material and preparation method thereof |
| WO2022042605A1 (en) * | 2020-08-26 | 2022-03-03 | 山东省联合农药工业有限公司 | Bactericidal composition comprising pyrazole amide compound and triazole bactericide |
Non-Patent Citations (2)
| Title |
|---|
| Synthetic and biological studies on some new camphor thiazolidinones;Ahmed M. Abo-Bakr et al.;《Journal of the Iranian Chemical Society》;第18卷(第10期);1-13 * |
| 氨基硫脲和D-樟脑磺酸钠手性镧系配合物的合成与表征;马红竹, 王博, 史启祯;中国稀土学报(第04期);370-373 * |
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