CN110278956B - Light-operated bactericide for preventing and treating plant fungal diseases and application thereof - Google Patents
Light-operated bactericide for preventing and treating plant fungal diseases and application thereof Download PDFInfo
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- CN110278956B CN110278956B CN201910548613.1A CN201910548613A CN110278956B CN 110278956 B CN110278956 B CN 110278956B CN 201910548613 A CN201910548613 A CN 201910548613A CN 110278956 B CN110278956 B CN 110278956B
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5
Abstract
The invention belongs to the field of light-operated pesticide bactericides,the light-operated bactericide for preventing and treating plant fungal diseases has the structure shown in chemical structural formula I, and is prepared through oxidation cyclization, reduction, diazotization coupling and methylation reaction in sequence. The structure can generate photoisomerization after being irradiated by ultraviolet light, and the trans-configuration with low activity is converted into the cis-configuration with high activity, so that the drug activity can be regulated and controlled as required. After stopping light stimulation, the high-activity cis-structure can spontaneously weaken the activity along with the prolonging of time, and the accumulation of the active medicament in the environment can be reduced. The invention can overcome the defects of the traditional chemical pesticide bactericide which has high residue and is easy to generate drug resistance.
Description
Technical Field
The invention discloses a preparation method of a light-operated bactericide for preventing and treating plant fungal diseases and application of the light-operated bactericide in the aspect of light-operated plant pathogenic fungus resistance, belonging to the field of light-operated pesticide bactericides.
Background
Fungal diseases have been one of the most important factors limiting agricultural production, with crop yield losses caused by phytopathogenic fungi of up to 20% per year and further losses of 10% after harvest (Science,2018,360(6390): 739-. The use of chemical drugs is the most important means for controlling fungal diseases of crops at present. Generally, once applied, chemical pesticides have no conscious control of their activity, such that they still accumulate in the environment at high doses of the active ingredient after exerting a bactericidal effect. However, the constant accumulation of active drugs in the environment leads to many adverse side effects, such as resistance, toxicity to beneficial organisms, food safety, environmental pollution, etc. Therefore, how to skillfully design the pesticide bactericide molecules with controllable activity and accurately control the activity of the pesticide bactericide molecules to ensure that the pesticide bactericide molecules do not affect other environments after exerting the pesticide effect is of great significance for safe application of the pesticide molecules and slowing down the generation of resistance.
In the field of medicine, the biological activity of drug molecules is controlled by using an optical switch, so that the environmental toxicity of the drug and the drug resistance of pathogenic bacteria can be reduced, and the precise control of the drug activity can be realized (Nature Chemistry,2013,5(11): 924-928). The idea has been remarkably developed in the field of medicine, such as light-controlled antibiotics, light-controlled antitumor drugs, light-controlled enzyme inhibitors, and the like. Therefore, the optical switch is introduced into the active group of the pesticide bactericide, and the design of the optical controllable pesticide molecules can certainly promote the development of environment-friendly pesticides, thereby effectively solving the defects of high residue, easy generation of resistance and the like of the existing pesticides.
1,3, 4-oxadiazole is a nitrogen-containing and oxygen-containing heterocyclic group with various biological activities, is an important component in a plurality of pharmaceutically active molecular structures, and is also widely applied to the structural design of pesticide bactericide molecules. Azobenzene and its derivatives have been attracting attention as a photoswitch. Because of the advantages of easy synthesis, high photoisomerization efficiency, rapid reversible conversion between isomers and the like, azobenzene or derivatives thereof are widely applied to the biological function regulation and control of active molecules as photoswitches. However, there is no report on the regulation of the activity of azobenzene-containing derivatives against plant pathogenic fungi.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and introduces a light control thought into the design of agricultural antibacterial molecules. The 1,3, 4-oxadiazole group of the antibacterial active pharmacodynamic fragment is combined with the photoswitch azobenzene group to synthesize the 1,3, 4-oxadiazole azobenzene derivative with a light-operated structure. The natural factor-light is used to control the opening and closing of the activity of the compound, and the precise and controllable activity of the pesticide antibacterial molecules is realized.
In order to achieve the above objects, the present invention provides a photo-fungicide for controlling fungal diseases of plants, namely (3, 4-dimethoxy-phenyl) - {4- [5- (3,4, 5-trimethoxy-phenyl) - [1,3,4] oxadiazol-2-yl ] -phenyl } -diazene, which has the chemical structural formula shown below:
the invention also provides a preparation method of the light-operated bactericide for preventing and treating the plant fungal diseases, which takes N- (3,4, 5-trimethoxy benzyl) -4-nitrobenzoylhydrazone as a raw material to prepare the light-operated bactericide for preventing and treating the plant fungal diseases through an oxidation cyclization reaction, a reduction reaction, a diazotization coupling reaction and a methylation reaction. The method specifically comprises the following steps:
the light-operated bactericide for preventing and treating plant fungal diseases is used for preventing and treating plant pathogenic fungal diseases, and comprises botrytis cinerea, fusarium graminearum and colletotrichum gloeosporioides.
The wavelength of the light-operated light source used by the invention is 365-380 nm; the illumination time is once every 4-6 h, and each illumination time is 2-5 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the bactericide of the invention has the advantages of simple preparation, easily obtained raw materials, mild reaction conditions and suitability for popularization and application.
2. The bactericide obtained by the invention can generate photoisomerization after being irradiated by ultraviolet light, and is converted from a trans-configuration with low activity into a cis-configuration with high activity, namely, the activity of the medicament can be controlled by the irradiation of the ultraviolet light, so that the control of medicament molecules on the aspect of preventing and controlling crop diseases can be realized according to the requirement.
3. The bactericide prepared by the invention can automatically weaken the activity after stopping light stimulation, and the cis-form structure with high activity is spontaneously converted into the trans-form structure with low activity along with time, thereby having positive effects on reducing the accumulation of active drugs in the environment and weakening the drug resistance of pathogenic microorganisms. Overcomes the defects of high residue, high pollution, easy generation of drug resistance and the like of the common active bactericide.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the fungicide of the present invention, wherein (a) a hydrogen spectrum and (b) a carbon spectrum.
FIG. 2 is a high resolution mass spectrum of the fungicide of the present invention.
FIG. 3 shows the changes of the ultraviolet-visible spectrum and the hydrogen spectrum of nuclear magnetic resonance before and after the irradiation of light, wherein (a) the ultraviolet-visible spectrum and (b) the hydrogen spectrum.
FIG. 4 is an in vitro inhibitory activity of the fungicides of the present invention against Botrytis cinerea, wherein (a) illuminated blank, (b) illuminated 200. mu.g/mL fungicide, (c) illuminated 100. mu.g/mL fungicide, (d) non-illuminated blank, (e) non-illuminated 200. mu.g/mL fungicide, and (f) non-illuminated 100. mu.g/mL fungicide.
FIG. 5 is a graph of the in vivo control efficiency of the fungicides of the present invention against Botrytis cinerea, wherein (a) a blank control of light, (b) no light fungicide treatment, and (c) light fungicide treatment.
Detailed Description
The invention is further described with reference to the following specific embodiments and the accompanying drawings. It should be noted that the embodiments described below are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without making any inventive step, shall fall within the scope of protection of the claims of this application.
Example 1: preparation of 2- (4-nitro-phenyl) -5- (3,4, 5-trimethoxy-phenyl) - [1,3,4] oxadiazole,
oxidation cyclization reaction: in a 150mL two-necked round-bottomed flask, 2g (5.56mmol) of N- (3,4, 5-trimethoxybenzyl) -4-nitrobenzoylhydrazone as a starting material and 30mL of anhydrous ethanol were added, and the mixture was stirred at 70 ℃ until it was dissolved. 7.8g (27.80mmol) of chloramine T (4g +3.8g, 2h apart) were added in two portions and stirred at 80 ℃ under reflux. And (3) monitoring the reaction by a point plate, after the reaction is finished, carrying out suction filtration to remove impurities while the reaction is hot, taking the filtrate, carrying out reduced pressure evaporation to remove the solvent, adding a small amount of distilled water to wash out, carrying out suction filtration and washing, recrystallizing the obtained crude product with EtOH, and drying to obtain 1.15g of yellow powdery solid with the yield of 58%.
Example 2: preparation of 4- [5- (3,4, 5-trimethoxy-phenyl) - [1,3,4] oxadiazol-2-yl ] -aniline,
reduction reaction: 2g (5.60mmol) of the product obtained in example 1 were taken in a 150mL flask and CaCl was added215mL of aqueous solution (8g/50mL of water) and 50mL of DMF as a solvent. Stirring until dissolved, adding zinc powder 5.46g (84mmol), and mixing at 100 deg.CRefluxing for 8 h. The reaction solution was filtered while hot, the filtrate was poured into a beaker containing 100mL of ice water, placed in a refrigerator (5 ℃ C.) and left to stand overnight, filtered to give a crude product, which was then recrystallized from a mixed solvent of DMF/ethanol to give 1.43g of a yellow solid in 78% yield.
Example 3: preparation of (3, 4-dimethoxy-phenyl) - {4- [5- (3,4, 5-trimethoxy-phenyl) - [1,3,4] oxadiazol-2-yl ] -phenyl } -diazene,
the contents of the components are as follows:
1. diazotization coupling reaction: 200mg (0.61mmol) of the product obtained in example 2 was taken, 2.0mL of HCl (1M) and 5mL of water were added, and the mixture was stirred at 50 ℃ until dissolved. Then transferring to 0-5 ℃ ice salt bath, slowly dripping NaNO2Aqueous solution (46mg in 5mL water) and the mixture continues to react at this temperature for 1h to complete the diazotization. The resulting diazonium salt was added dropwise to an ethanolic o-methoxyphenol solution (84mg,0.67mmol in 5mL ethanol) at 0-5 deg.C. After the dropwise addition, the pH of the solution is adjusted to 8-9 by using 1M NaOH, and the obtained mixed solution is continuously reacted for 2 hours to complete the coupling reaction. Filtering, washing with water for 2 times, and drying to obtain the azophenol.
2. Methylation reaction: 200mg (0.44mmol) of the azophenol product obtained in step 1 is dissolved in 20mL of THF solvent, and K is added under stirring2CO3212mg (1.54mmol) and 315mg (2.22mmol) of methyl iodide were reacted at room temperature for 3 days. The solvent is removed by rotary evaporation, the crude product is dissolved by 20mL of DCM, and then is washed by saturated sodium bicarbonate and saturated saline in turn, and the yellow solid 178mg of the final product is obtained after column chromatography separation after drying by anhydrous magnesium sulfate, and the yield is 85%.1H NMR(400MHz,DMSO-d6)δ8.35(d,J＝8.5Hz,Ph-H,2H),8.05(d,J＝8.5Hz,Ph-H,2H),7.68(dd,J＝8.5,2.0Hz,Ph-H,1H),7.51(d,J＝2.0Hz,Ph-H,1H),7.43(s,Ph-H,2H),7.21(d,J＝8.6Hz,Ph-H,1H),3.94(s,OCH3-H,6H),3.90(s,OCH3-H,3H),3.88(s,OCH3-H,3H),3.79(s,OCH3-H,3H).13C NMR(101MHz,DMSO-d6)δ154.00,150.02,128.44,123.57,122.04,118.87,104.77,102.28,56.76.HRMS(ESI),m/z calcd for C25H25N4O6[M+H]+477.1769；found,477.1764。
Example 4: photoisomerization of the obtained germicide of the present invention
1. Ultraviolet spectrum determination: the product obtained in example 3 was dissolved in DMSO to prepare a test solution with a concentration of 30. mu.M. And 3mL of the prepared solution to be detected is added into a quartz cuvette, and an ultraviolet-visible absorption spectrum of the target molecule is recorded by an ultraviolet spectrophotometer. Then irradiating the solution for 2min by using an ultraviolet light source (365nm) to isomerize the structure of the compound, and recording an ultraviolet-visible absorption spectrum of the solution by using an ultraviolet spectrophotometer. And finally, placing the target molecule solution in a room under natural light conditions, and recording the ultraviolet visible absorption spectrum of the target molecule solution by using the spectrophotometer after 12 hours.
As shown in FIG. 3a, after the bactericide prepared by the invention is irradiated by ultraviolet light, the intensity of a pi-pi + transition absorption peak at 390nm is obviously reduced, which shows that the bactericide of the invention generates an isomerization phenomenon and is converted from a trans form to a cis form. Then, the optical isomerization reaction solution is placed under natural light conditions, and the pi-pi transition absorption peak at 390nm gradually recovers towards the peak position before illumination along with the time extension, thereby illustrating the reversibility of the optical isomerization process of the compound.
2. Nuclear magnetic hydrogen spectrum determination: dissolving the bactericide obtained by the invention in deuterated DMSO to prepare a solution to be detected of 10mg/mL, recording the nuclear magnetic spectrum of a target molecule by using a nuclear magnetic resonance spectrometer, irradiating the solution for 2min by using an ultraviolet light source (365nm) to enable the solution to reach a cis-form photostability, and recording the nuclear magnetic spectrum again.
As shown in fig. 3b, after 2min of ultraviolet irradiation, the intensity of the original signal peak of the compound is weakened, and a new hydrogen atom signal peak appears in the high field direction near the original signal peak, which also indicates that the compound of the present invention has cis-trans isomerism after being irradiated by ultraviolet light, and a cis-structure of the molecule is generated.
Example 5: the light-operated in-vitro activity of the bactericide obtained by the invention to plant pathogenic fungi is determined
In the test example, the inhibitory activity of the bactericide of the present invention against botrytis cinerea, fusarium graminearum and colletotrichum gloeosporioides is determined by a hypha growth rate method.
The experimental method comprises the following steps: the bactericide of the present invention was dissolved in a small amount of DMSO (final concentration of 0.5%, v/v) and the mother liquor was diluted with 0.1% Tween aqueous solution to a final concentration of 2000, 1000. mu.g/mL. 1mL of the liquid medicine with each concentration is respectively transferred by a liquid transfer gun and added with 9mL of melted PDA culture medium to be uniformly mixed, and the mixture is poured into a disposable culture dish (9cm) to prepare a medicine-containing flat plate. A cake of 5mm diameter was taken from the edge of a round of hyphae cultured on PDA and placed in the center of a solidified drug-containing plate with the hyphae facing downward. The inoculated plate was transferred to a constant temperature incubator and incubated at 25 ℃. And when the blank control hyphae grow over the whole flat plate, measuring the hyphae growth diameter on each flat plate, and calculating the inhibition rate of each treatment group on the hyphae growth.
Light control conditions: the treatment is repeated in three groups, the first group is treated without light, and the second group is irradiated with 365nm ultraviolet light for 2min before the drug-containing plate is inoculated. The third group was illuminated every 6h (2 min each) on the basis of the second group. The same dose of DMSO was used as a blank control, and the light treatment was the same as the drug treatment.
TABLE 1 light-controlled in vitro antibacterial Activity of the fungicides of the present invention against phytopathogenic fungi
The test results are shown in fig. 4, and it can be seen from fig. 4 and table 1 that the bactericide of the present invention shows a distinct photoactivation phenomenon every 6 hours of light irradiation. Taking Botrytis cinerea as an example, the activity of the light group is nearly 3 times that of the non-light group every 6 hours at a concentration of 200. mu.g/mL. Meanwhile, the antibacterial activity of the photoactivatable target molecules is far smaller than that of target molecules subjected to multiple times of illumination, which shows that the photoactivatable cis-configuration can spontaneously convert to the low-activity trans-configuration after illumination stimulation is stopped, and a thought is provided for controlling the activity of pesticide molecules according to needs. When the drug effect is required, the drug activity can be activated by light. After the drug effect is exerted, the activity of active molecules in the environment can be automatically weakened, the characteristic can greatly reduce the residue of active drug molecules in the environment, and the drug has positive effects on solving the problems of microbial drug resistance, food safety and environment.
Example 6: the light-operated in-vivo prevention and treatment efficiency of the bactericide on botrytis cinerea
In this test example, the in vivo antibacterial activity of the bactericide of the present invention against Botrytis cinerea was measured by a tomato live transfer method.
The experimental method comprises the following steps: according to Standard Operation Protocol (SOP) for measuring biological Activity of pesticides, the compound is dissolved in a small amount of DMSO, and then diluted with 0.1% Tween aqueous solution to obtain a liquid medicine with a concentration of 200 μ g/mL. Fresh tomato fruits were disinfected by wiping the surface with 75% alcohol and rinsed clean with sterile water. After the residual flushing liquid on the surface of the fruit is naturally air-dried, the liquid medicine is uniformly sprayed on the surface of the fruit and is air-dried under natural conditions. Pricking epidermis with diameter of 5mm in the middle of the fruit with a sterilized inoculating needle, and clamping the Botrytis cinerea cake with diameter of 5mm on the surface of the wound with sterilized forceps. The inoculated fruit was then incubated in an incubator at 25 ℃ and 90% relative humidity. And after the hyphae of the blank control group fully grow, measuring the growth diameter of the hyphae treated by each medicament, and calculating the control efficiency of each medicament treatment.
Light control conditions: two groups of drug treatments were set for this experiment, one group was irradiated with a 380nm UV light source (5min each time every 4 h) and the other group was not irradiated with light. The blank was treated with the same dose of solvent and with the same light.
TABLE 2 light-operated in vivo control efficiency of the fungicides of the present invention against Botrytis cinerea
| Serial number | Control Effect (%, 200. mu.g/mL) on Botrytis cinerea |
| I-no illumination | 23.3 |
| I-illumination | 49.2 |
As shown in FIG. 5, it is understood from the results of the tests in combination with FIG. 5 and Table 2 that after 5 days of incubation at constant temperature and humidity, the surface of the tomato of the blank group was almost covered with Botrytis cinerea hyphae under light conditions. The growth of botrytis cinerea hyphae on the surfaces of tomatoes sprayed with the medicine without illumination is slightly weaker than that of blank control, and the control effect on the botrytis cinerea hyphae is 23.3 percent through control effect calculation. However, after the spraying treatment of the medicine is carried out once every 4 hours of illumination (every 5min), the growth of botrytis cinerea is obviously inhibited, and the control effect reaches 49.2 percent, which shows that the bactericide has obvious light-operated control effect on tomato botrytis cinerea.
In the field of medicine, the study of combining antibacterial active fragment quinolone with photoswitch azobenzene to form photoisomerizable azoquinolone is carried out in the early stage. The structure can obviously improve the in vitro antibacterial activity to human pathogenic bacteria under the stimulation of ultraviolet light and can be gradually inactivated after the stimulation is stopped (Nature Chemistry,2013,5(11): 924-928). The light-operated bactericide can obviously improve the in-vitro and in-vivo antibacterial activity to plant pathogenic fungi under the stimulation of ultraviolet light, and can spontaneously weaken the activity after the stimulation is stopped. The method also provides a new idea for the practical application possibility of the light-operated bactericide in the field of pesticide bactericides. The invention is suitable for the greenhouse for planting the fruits and the vegetables, the light source of which can be controlled.
Claims (6)
1. The light-operated bactericide for preventing and treating plant fungal diseases is characterized by having the following chemical structural formula:
2. the use of the light-operated fungicide according to claim 1 for controlling fungal diseases of plants.
3. Use according to claim 2, wherein the light-controlled light source is ultraviolet light.
4. The use according to claim 2, wherein the light source wavelength of the light control comprises 365-380 nm.
5. Use according to claim 3 or 4, characterized in that the conditions of the light control are: the illumination time is once every 4-6 h, and each illumination time is 2-5 min.
6. The use according to claim 5, wherein the plant fungi include Botrytis cinerea, Fusarium graminearum and Colletotrichum.
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| IL73611A0 (en) * | 1983-12-06 | 1985-02-28 | Nippon Soda Co | 1,2,4-oxa-and thiadiazolin-3-one derivatives,their preparation and their use as insecticides and fungicides |
| JPS61275271A (en) * | 1985-05-30 | 1986-12-05 | Nippon Soda Co Ltd | 1,2,4-oxa(thia)diazoline derivative, production thereof and insecticide and agricultural and horticultural germicide |
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