CN112602714B - Application of fludioxonil carboxylic acid derivatives in plant vascular tissue targeting medicament - Google Patents
Application of fludioxonil carboxylic acid derivatives in plant vascular tissue targeting medicament Download PDFInfo
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- CN112602714B CN112602714B CN202011538909.4A CN202011538909A CN112602714B CN 112602714 B CN112602714 B CN 112602714B CN 202011538909 A CN202011538909 A CN 202011538909A CN 112602714 B CN112602714 B CN 112602714B
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- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The invention discloses application of fludioxonil carboxylic acid derivatives in plant vascular tissue targeting medicaments. The carboxylic acid group modification is carried out on the non-systemic bactericide fludioxonil, so that the obtained fludioxonil carboxylic acid derivative shows good plant phloem conductivity, and can be used as a plant vascular tissue targeting bactericide. The fludioxonil carboxylic acid derivative provided by the invention has good prevention and treatment effects when being used for preventing and treating banana vascular wilt.
Description
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to application of fludioxonil carboxylic acid derivatives in plant vascular tissue targeted medicaments.
Background
As a world's leading country of bananas, banana wilt is reported in all banana leading areas in China, thereby bringing devastating attack to the banana industry in China and becoming the most important factor restricting the development of the banana industry in China. Banana vascular wilt is a soil-borne vascular bundle disease caused by Fusarium oxysporum cubeba specialization (Fusarium oxysporum f.sp.cubense, Foc), with pathogenic bacteria invading the xylem of banana root system and subsequently proliferating in banana vascular tissue (xylem and phloem). As a destructive plant disease, the control of banana vascular wilt has been a worldwide problem. Once pathogenic bacteria invade the vascular tissue of bananas, the traditional bactericide cannot directly act on the pathogenic bacteria, which also becomes a main reason that the chemical control of the banana vascular wilt is difficult to work.
A plurality of existing bactericides show excellent bacteriostatic activity on banana vascular wilt germs in indoor in vitro conditions, but the control effect in fields is poor, so that no bactericides approved for controlling banana vascular wilt are registered in China at present. The existing systemic bactericide mainly has xylem systemic property, namely, the systemic bactericide is shown in that along with the transpiration tension conduction of xylem, the systemic bactericide can be rapidly accumulated to parts with vigorous transpiration, such as plant leaves, but is difficult to accumulate in plant vascular tissues, and the dosage which can really reach the harmful parts is very low. Meanwhile, once pathogenic bacteria invade the xylem, the transpiration flow is blocked, and the conduction of the medicament is blocked. On the contrary, the systemic property of the phloem can realize the conduction of the bactericide from leaves to roots, and the medicine can not only form wider distribution in the root system of the plant body through a symplast way, but also can not lose the conduction capability due to the infection of pathogenic bacteria.
Different from xylem, plant phloem (sieve tube and parasporal) is composed of living cells, has strong selectivity, so far, no fungicide variety with good phloem systemic property exists in the market, and the research and development of pesticides with phloem conductivity have become a new direction for pesticide research and development. Among them, structural optimization based on the phloem "ion well" effect has been proven to be one of the effective approaches to develop phloem-conductive agents.
Fludioxonil has an antibacterial effect on banana fusarium wilt bacteria under the in vitro condition. The fludioxonil carboxylic acid derivative can be used as a CRTH2 receptor antagonist (Chinese patent publication CN 101072773B) for medicine application, but the effect of the fludioxonil carboxylic acid derivative as a target bactericide for vascular tissues with banana vascular wilt is not reported.
Disclosure of Invention
The invention aims to provide application of fludioxonil carboxylic acid derivatives in plant vascular tissue targeting medicaments, aiming at the defect that no bactericide with good phloem conductivity exists in the prior art.
The invention discloses a new application of an arylpyrrole bactericide containing carboxylic acid groups in preventing and treating banana wilt. The compound can enter plant vascular tissues in a targeted mode through an ion well effect and is conducted to bulbs and roots in banana plants so as to be used for preventing and treating banana wilt.
It is therefore a first object of the present invention to provide: the application of the compound shown in the formula I or the formula II or the salt thereof in a plant vascular tissue targeting medicament,
wherein R in the formula I1Is H or CH3N is 0 or 1; in the formula II R1Is H or CH3And n is 0 or 1.
Preferably, in the application, the plant vascular tissue targeting medicament is a banana vascular tissue targeting bactericide.
Preferably, in the application, the plant vascular tissue targeting agent is a precursor bactericide for preventing and treating banana vascular wilt.
Preferably, the application is to use the plant vascular tissue targeting agent for preventing and treating banana vascular wilt.
The invention also provides a plant vascular tissue targeting agent, which comprises an effective amount of the compound shown in the formula I or the formula II or the salt thereof and a carrier acceptable in pesticides.
The invention also provides a method for preventing and treating banana vascular wilt, which comprises applying an effective amount of the compound shown in the formula I or the formula II or the salt thereof to banana plants.
The fludioxonil carboxylic acid derivative obtained by modifying the non-systemic bactericide fludioxonil with carboxylic acid groups shows good systemic conductivity in the phloem of the plant, can realize the conduction of the bactericide from leaves to roots, and can be used as a plant vascular tissue targeted bactericide. The fludioxonil carboxylic acid derivative provided by the invention has good prevention and treatment effects when being used for preventing and treating banana vascular wilt.
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Fig. 1 is a synthetic route for the preparation of fludioxonil carboxylic acid derivatives of example 1, wherein compounds 1b, 2b, 3b and 4b correspond in sequence to fludioxonil carboxylic acid derivatives 1b, 2b, 3b and 4b, and compounds 1a, 2a, 3a and 4a correspond in sequence to fludioxonil carboxylic acid derivatives 1a, 2a, 3a and 4 a.
FIG. 2 is a test of the phloem conductance of castor seedlings with the fludioxonil carboxylic acid derivatives prepared in example 1, wherein compounds 1b, 2b, 3b and 4b correspond to fludioxonil carboxylic acid derivatives 1b, 2b, 3b and 4b in sequence, and compounds 1a, 2a, 3a and 4a correspond to fludioxonil carboxylic acid derivatives 1a, 2a, 3a and 4a in sequence.
FIG. 3 shows phloem conductance of fludioxonil carboxylic acid derivative 1a under different external pH conditions.
FIG. 4 shows the potting controlling effect of fludioxonil carboxylic acid derivative 1a on banana vascular wilt bacteria (Foc 4).
FIG. 5 shows the delivery and release of fludioxonil carboxylic acid derivative 1a at each site on banana plants, wherein fludioxonil prodrug is a control group and 1a represents fludioxonil carboxylic acid derivative 1 a.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1: chemical synthesis and structural identification of fludioxonil carboxylic acid derivatives 1a and 1b
The experimental method comprises the following steps: as shown in the synthetic route of figure 1, fludioxonil is dissolved in acetonitrile (CH)3CN) solution, adding cesium carbonate (Cs)2CO3) And tetrabutylammonium iodide (TBAI) and stirred at room temperature for 1 h. Methyl bromoacetate was then added dropwise, and the reaction flask was transferred to an oil bath and heated to 80 ℃ with stirring. And after the reaction of the raw materials is finished, adding 1mol/L hydrochloric acid solution to adjust the reaction solution to be acidic (pH is 2), extracting with ethyl acetate for three times, washing with saturated sodium chloride solution, concentrating under reduced pressure, and separating by column chromatography to obtain the target compound 1 b.
The objective Compound 1b was dissolved in Tetrahydrofuran (THF) and water (H)2O) mixed solution, adding lithium hydroxide monohydrate (LiOH-H) at low temperature of 0 DEG C2O), stirred at room temperature overnight. After the reaction is completed, 1mol/L hydrochloric acid solution is added to adjust the pH value of the reaction solution to acidity (pH is 2), ethyl acetate is used for extraction for three times, and the target compound 1a is obtained after drying and concentration.
The experimental results are as follows: target Compounds 1a and 1b by NMR1H NMR), nuclear magnetic resonance carbon (C: (M:)13C NMR) and high resolution mass spectrometry, the data are shown in table 1.
TABLE 1 structural identification data of fludioxonil carboxylic acid derivatives 1a, 1b
Thus, the target compound 1b was identified as a fludioxonil carboxylic acid derivative 1b, having the following chemical formula:
wherein R in the formula I1Is H, and n is 0.
Determining the target compound 1a as a fludioxonil carboxylic acid derivative 1a, wherein the chemical structural formula is as follows:
wherein R in the formula II1Is H, and n is 0.
According to a similar preparation method (a synthetic route shown in figure 1) and structural characterization by the same method, fludioxonil carboxylic acid derivatives 2b, 3b and 4b and corresponding fludioxonil carboxylic acid derivatives 2a, 3a and 4a are prepared correspondingly.
The chemical structural formula of the fludioxonil carboxylic acid derivatives 2b, 3b and 4b is as follows:
wherein fludioxonil carboxylic acid derivative 2b corresponds to R in formula I1Is CH3N is 0;
fludioxonil carboxylic acid derivative 3b corresponds to R in formula I1Is H, n is 1;
fludioxonil carboxylic acid derivative 4b corresponding to R in formula I1Is CH3And n is 1.
The chemical structural formula of the fludioxonil carboxylic acid derivatives 2a, 3a and 4a is as follows:
wherein fludioxonil carboxylic acid derivative 2a corresponds to R in formula II1Is CH3N is 0;
fludioxonil carboxylic acid derivative 3a corresponds to R in formula II1Is H, n is 1;
fludioxonil carboxylic acid derivative 4a corresponds to R in formula II1Is CH3And n is 1.
Example 2: delivery of fludioxonil carboxylic acid derivatives prepared in example 1 to phloem of model plant Castor plant seedlings
The experimental method comprises the following steps: the castor bean seedlings are model plants for phloem conductance research, and are widely used for screening and evaluating the conductance of pesticides in phloems of plants.
In this example, the phloem conductance evaluation of the fludioxonil carboxylic acid derivative synthesized in example 1 was performed by immersing castor leaf in a buffer solution containing 20mmol/LMES (pH 5.0), adding fludioxonil carboxylic acid derivative (1a, 2a, 3a, 4a, 1b, 2b, 3b, and 4b) to be tested at a final concentration of 0.1mmol/L, treating the castor leaf for 2 hours, cutting the hypocotyl, and collecting phloem fluid exuded from the cut within 2 hours. The collected phloem solution was diluted with acetonitrile and analyzed by High Performance Liquid Chromatography (HPLC). The experiment was repeated 3 times with fludioxonil (technical drug) as a control group, 4 seedlings per dose were treated each time and each dose was tested separately.
The experimental results are as follows: the result is shown in fig. 2, the non-systemic fungicide fludioxonil is not detected in the phloem liquid of castor bean, which shows that the fludioxonil has no phloem conductance; after carboxylic acid group modification, fludioxonil carboxylic acid derivatives 1a, 2a, 3a and 4a all appear in phloem fluid, and show good phloem conductance of plants. The derivative compounds (1b, 2b, 3b and 4b) of the methyl carboxylate have no phloem output conductivity, which indicates that the ionization of the carboxylic acid group is important for the phloem output conductivity of the compound, and the introduction of the carboxylic acid function enables the compound to have the phloem output conductivity, so that the fludioxonil carboxylic acid derivative can be used as a plant vascular tissue targeting bactericide.
Example 3: phloem conductance of fludioxonil carboxylic acid derivative 1a without extraplasmic pH
The experimental method comprises the following steps: the castor leaf is immersed in a buffer solution containing 20mmol/L MES (pH 5.0 and 6.0) or 20mmol/L HEPES (pH 7.0 and 8.0), and simultaneously, a fludioxonil carboxylic acid derivative to be tested is added to the buffer solution at a final concentration of 0.1mmol/L, after the castor leaf is treated for 2 hours, the hypocotyl is cut, and phloem liquid exuded from the cut within 2 hours is collected. The collected phloem solution was diluted with acetonitrile and analyzed by High Performance Liquid Chromatography (HPLC). The experiment was repeated 3 times, 4 seedlings per dose were treated and each was tested individually.
The experimental results are as follows: as a result, as shown in FIG. 3, the concentration of fludioxonil carboxylic acid derivative 1a in phloem gradually decreased with the increase in pH of the culture broth, and the phloem concentration decreased by about 20 times from pH 5.0 to 8.0. The castor seedling cotyledon has an open apoplast space, the pH value of the apoplast is influenced by the pH value of an external culture solution, and the result shows that the ion well effect is the main mechanism that the fludioxonil carboxylic acid derivative 1a has phloem conductance. From this, it is presumed that the other fludioxonil carboxylic acid derivatives 2a, 3a and 4a also have the same transport mechanism.
Example 4: potted plant efficacy experiment of fludioxonil carboxylic acid derivative on banana wilt
The experimental method comprises the following steps: applying 0.8mmol/L of fludioxonil carboxylic acid derivative 1a, 1b, 2a, 2b, 3a, 3b, 4a and 4b to be tested to banana plants by a leaf coating method in two times, and applying the medicines 2 days before and 5 days after soil inoculation respectively; the control group was treated with the same aqueous blank solution; the fludioxonil treatment group was the same treatment as described above with 0.8mmol/L fludioxonil as the drug substance. Shaking banana Fusarium oxysporum (Fusarium oxysporum f.sp. cubense) Foc4 with YPD liquid culture medium to produce spores, wherein each banana has root system perfused with 1 × 106The spore suspension is 100mL per mL, the disease index of the bananas is investigated after 40 days, the control effect is calculated, and the experiment is repeated for 3 times, wherein each time, 6 bananas are treated.
The experimental results are as follows: as shown in fig. 4, the incidence of fludioxonil carboxylic acid derivative 1a treated banana plants was significantly lower than the control and fludioxonil treated groups, with only the lower leaves partially yellowing. Significant large areas of dark brown lesions were found in the banana bulbs of the control and fludioxonil-treated groups, whereas the bulbs of the fludioxonil carboxylic acid derivative 1 a-treated group showed no or only slight discoloration at the edges, indicating that the disease infestation was significantly lower than in the control and fludioxonil-treated groups.
The other fludioxonil carboxylic acid derivatives show good control effect on banana vascular wilt after potted plant activity experiments are carried out by the same method. As shown in table 2, the disease index of the fludioxonil carboxylic acid derivative 1 a-treated group was 27.8%, which was significantly lower than 61.1% and 56.9% of the control and fludioxonil-treated groups, and the best control effect was exhibited. And the control effects of the fludioxonil carboxylic acid derivatives 1a, 1b, 2a, 2b, 3a, 3b, 4a and 4b are better than those of the fludioxonil treatment group.
TABLE 2 potted-plant control Effect of fludioxonil carboxylic acid derivatives prepared in example 1 on banana vascular wilt disease (Foc4)
Example 5: transduction degradation of fludioxonil carboxylic acid derivatives 1a on banana plants
The experimental method comprises the following steps: applying 0.2mmol/L fludioxonil carboxylic acid derivative 1a to the middle leaves of bananas by a leaf coating method, and coating two leaves on each banana; the fludioxonil treatment group was prepared by performing the same treatment as above with 0.2mmol/L fludioxonil as a control. Collecting the upper leaves, the application leaves, the pseudostems, the corms and the roots of the banana plants respectively 2, 5, 7, 10 and 14 days after the application of the fludioxonil, analyzing by adopting a liquid chromatography tandem mass spectrometer, and detecting the concentrations of the test compound fludioxonil carboxylic acid derivative 1a and the fludioxonil which is possibly degraded. 3 bananas at each time point, and the concentration of each part of the pesticide is detected respectively.
The experimental results are as follows: the result is shown in fig. 5, the systemic property of fludioxonil on banana plants is very limited, only weak upward conductivity is found, and the ability of conducting towards corms and roots is not found, which indicates that fludioxonil only has certain xylem systemic property and does not have phloem systemic property. In contrast, the fludioxonil carboxylic acid derivative 1a exhibits bidirectional conductivity in banana bodies and can be gradually degraded to release fludioxonil. After the fludioxonil carboxylic acid derivative 1a is applied to the leaves, it can be transmitted down to the banana bulb and roots through the phloem, where the parent compound fludioxonil, which originally could not be transported over long distances, is detected, and the bulb reaches the peak concentration after 5d of application. The above results indicate that the improvement of phloem conductance of the agent enables the agent to be delivered to the banana bulb and root, and at the same time, fludioxonil carboxylic acid derivative 1a exhibits prodrug properties.
Claims (6)
1. The application of the compound shown in the formula I or the formula II or the salt of the compound shown in the formula II in the plant vascular tissue targeting medicament,
wherein R in the formula I1Is H or CH3N is 0 or 1; in the formula II R1Is H or CH3And n is 0 or 1.
2. The use of claim 1, wherein the plant vascular tissue-targeting agent is a banana vascular tissue-targeting bactericide.
3. The use of claim 1, wherein the plant vascular tissue-targeting agent is a precursor fungicide for the control of banana vascular wilt.
4. The use of claim 1, wherein said plant vascular tissue targeting agent is used for the control of banana vascular wilt.
5. A plant vascular tissue targeting agent comprising an effective amount of a compound of formula I or formula II, or a salt of a compound of formula II, according to claim 1, and a pesticidally acceptable carrier.
6. A method for controlling banana vascular wilt, comprising applying an effective amount of a compound of formula I or formula II, or a salt of a compound of formula II, as defined in claim 1 to a banana plant.
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