Azobenzene calix [4] arene derivative as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to azobenzene calix [4] arene derivatives as well as a preparation method and application thereof. The invention discloses a novel azobenzene calix [4] arene derivative prepared by directional modification through an azo reduction reaction based on a calix [4] arene skeleton. The azobenzene calix [4] arene derivative has the characteristics of green environmental protection, accurate and controllable structure and efficient synthesis. After the derivative and a pesticide form a host-guest compound, the activity of the pesticide can be remarkably improved, the bioavailability of the pesticide at an action site is increased, the problem of low efficiency of the traditional pesticide is effectively solved, and the development of target drug resistance is delayed. The technology breaks through the technical bottleneck of nano-carrier environmental toxicity, provides a new thought for developing a multi-target and low-environmental-risk pesticide synergist, and has important significance for realizing pesticide decrement, synergism and resistance treatment.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of pesticides. More particularly, it relates to a kind of azobenzene calix[4]arene derivatives and its preparation method and application. BACKGROUND

[0002] In agricultural production, bacterial diseases such as cucumber bacterial angular spot (Pseudomonas syringae pv. lachrymans) and rice bacterial leaf blight (Xanthomonas oryzae pv. oryzae) seriously threaten crop health, leading to leaf necrosis, plant wilting and even absolute yield. At present, chemical pesticide formulations are still the main means to prevent and control such diseases, but traditional formulations have many problems in practical application, which seriously restricts their prevention and control effect and environmental sustainability.

[0003] Traditional formulations such as copper formulations, antibiotics and organic sulfur compounds generally have poor water solubility, which requires the assistance of organic solvents or surfactants for dissolution, resulting in an effective ingredient utilization rate of less than 20%. Most of the agents cannot exert their efficacy due to leaf loss or volatilization. In addition, long-term single use of the same type of formulation accelerates the development of pathogen resistance, for example, the resistance rate of cucumber bacterial angular spot bacteria to copper formulations in some areas has exceeded 30%, significantly reducing the prevention and control effect. More seriously, about 80% of the pesticides are directly discharged into the environment during the application process, not only polluting the soil and water, disrupting the ecological balance of microorganisms, but also endangering human health through agricultural product residues, increasing liver and kidney toxicity and carcinogenic risk.

[0004] In recent years, in order to improve the utilization rate of pesticides, researchers have tried new delivery systems such as nano-carriers, microcapsules and slow-release technology. However, these technologies still have obvious defects. For example, nano-carriers (such as liposomes, polymer nanoparticles) are prone to aggregation or degradation in complex environments (such as soil, plant body fluids), resulting in premature release of drugs; the formation of bacterial biofilm further hinders drug penetration, making it difficult for conventional dosage forms to completely kill pathogens, leading to repeated occurrence of diseases. In addition, most of the pesticide synergists use traditional surfactants, which have poor biodegradability, can easily cause environmental pollution, and have limited effect on improving the efficacy and penetration of pesticides.

[0005] In view of the above problems, it is urgent to develop a new pesticide synergistic method that can improve drug utilization while being environmentally friendly, thereby effectively overcoming the low efficiency and environmental pollution problems of traditional pesticide formulations. SUMMARY

[0006] The technical problem to be solved by the present application is to overcome the defects and shortcomings of the low efficiency, drug resistance and environmental pollution of traditional pesticide formulations, and to provide a kind of azobenzene calix[4]arene derivative or its agronomically acceptable salt.

[0007] An object of the present application is to provide a method for preparing the azobenzo-calix[4]arene derivative or the agrologically acceptable salt thereof.

[0008] Another object of the present application is to provide the azobenzo-calix[4]arene derivative or the agrologically acceptable salt thereof as a pesticide synergist.

[0009] Another object of the present application is to provide a pesticide composition.

[0010] Another object of the present application is to provide an azobenzo-calix[4]arene complex.

[0011] Still another object of the present application is to provide a composition based on the azobenzo-calix[4]arene complex.

[0012] The above objects of the present application are achieved by the following technical solutions.

[0013] The present application protects a kind of azobenzo-calix[4]arene derivative or the agrologically acceptable salt thereof, the structure of the azobenzo-calix[4]arene derivative or the agrologically acceptable salt thereof is as shown in formula (I):

[0014]

[0015] In formula (I), the R 1 It is selected from -COOH, -SO3H, -SO2NH2 Or Wherein, -COOH is not substituted or substituted by substituent R 3 R 3 It is selected from X - Indicate anion;R 2 It is selected from hydrogen, C 1～6 Alkyl, halogenated C 1～6 Alkyl or halogen.

[0016] Compared with traditional cyclodextrin embedding agent, the azobenzo-calix[4]arene derivative or the agrologically acceptable salt thereof provided by the present application has the following advantages: 1) cavity size can be adjusted, can adapt macromolecular pesticide preparation;2) upper edge modification group enhances water solubility, reduces organic solvent dependence.

[0017] Further, the R 2 It is selected from hydrogen, C 1～3 Alkyl, halogenated C 1～3 Alkyl or halogen.

[0018] Still further, the C 1～3 Alkyl is preferably methyl.

[0019] Further, the halogen is selected from chlorine, bromine, fluorine or iodine, preferably chlorine.

[0020] Further, X represents halogen. Preferably, the halogen is selected from chlorine, bromine, fluorine or iodine, preferably chlorine.

[0021] Preferably, the azobenzene calix[4]arene derivative or its agriculturally acceptable salt is represented by any of the following structures:

[0022]

[0023] The present application protects a preparation method of the azobenzene calix[4]arene derivative or its agriculturally acceptable salt, comprising the following steps:

[0024] S1. A diazonium salt solution is prepared with compound 1, a solvent solution containing compound 2, sodium acetate or its hydrate is added, and a reaction is carried out to obtain target compound I-1;

[0025] S2. When R 1 selected from -COOH, and substituted by R 3 When R

[0026]

[0027] Further, the preparation method of the diazonium salt solution comprises the following steps: compound 2, sodium nitrite, hydrochloric acid and solvent are mixed and reacted under ice bath conditions to obtain a diazonium salt solution.

[0028] Further, in the preparation method of the diazonium salt solution, the solvent is selected from water and / or acetone.

[0029] Further, the hydrochloric acid is concentrated hydrochloric acid (37%, mass fraction).

[0030] Further, in step S1, the solvent at least contains N,N-dimethylformamide, and also includes methanol or water.

[0031] Further, the molar ratio of compound 1 to compound 2 is 1:(4-4.5).

[0032] Further, the molar ratio of compound 1 to sodium acetate or its hydrate is 1:(5-13).

[0033] Further, the mass-volume ratio of compound 1 to hydrochloric acid is 1g:(0.7-2)mL.

[0034] Further, in step S1, the temperature of the reaction is room temperature.

[0035] Further, the reaction time in step S1 is 2-5h.

[0036] Further, the solvent in step S2 is preferably N,N-dimethylformamide.

[0037] Further, the reaction in step S1 further comprises post-treatment.

[0038] Further, the condensing agent is preferably 2-(7-azabenzotriazol)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU).

[0039] Further, the organic base is preferably N,N-diisopropylethylamine (DIPEA).

[0040] Further, the molar ratio of compound I-1 and D-mannosamine hydrochloride is 1:(0.1-2).

[0041] Further, the molar ratio of compound I-1, condensing agent and organic base is 1:(0.4-0.6):(0.8-1.2).

[0042] The application protects the application of the azobenzene calix[4]arene derivative or its agronomically acceptable salt as a pesticide synergist.

[0043] The application protects an azobenzene calix[4]arene complex, which takes the azobenzene calix[4]arene derivative or its agronomically acceptable salt as a host compound and a pesticide as a guest compound, and obtains the host-guest combination.

[0044] The application provides a pesticide synergist taking azobenzene calix[4]arene as a core component. The synergist forms a stable inclusion compound with pesticide molecules through a unique molecular structure, which can significantly enhance the penetration ability of pesticides to targets and thus improve the pesticide efficacy. Meanwhile, azobenzene calix[4]arene has good biocompatibility and degradability, which can effectively reduce the potential pollution of pesticide residues to the environment, and is a new type of pesticide adjuvant with high efficiency and environmental protection.

[0045] Further, the azobenzene calix[4]arene complex is prepared by the following steps: mixing and uniformly mixing a solvent containing the azobenzene calix[4]arene derivative or its agronomically acceptable salt and a solvent containing a pesticide, fully combining, and drying to obtain the azobenzene calix[4]arene complex.

[0046] Further, the molar ratio of the azobenzene calix[4]arene derivative or the agrologically acceptable salt thereof and the pesticide is 1:(0.8-2), preferably 1:1.

[0047] Further, the solvent is preferably dimethyl sulfoxide.

[0048] Further, the time for sufficient combination is 20-30h.

[0049] Further, the drying is vacuum drying.

[0050] Preferably, the pesticide is a fungicide.

[0051] More preferably, the fungicide includes bixpyr, bromopyrole or pyrimethanil.

[0052] The present application protects a pesticide composition, which includes the azobenzene calix[4]arene complex and an agrologically acceptable adjuvant.

[0053] Compared with the prior art, the present application has the following beneficial effects:

[0054] The present application discloses a new azobenzene calix[4]arene derivative prepared by directional modification based on a calix[4]arene skeleton through an azo reduction reaction, which has the characteristics of green environmental protection, precise controllable structure and efficient synthesis. After the derivative and the pesticide form a host-guest complex, the activity of the pesticide can be significantly improved, the bioavailability of the pesticide at the action site can be increased, the problem of low efficiency of traditional pesticides can be effectively solved, and the development of target drug resistance can be delayed. The technology breaks through the technical bottleneck of environmental toxicity of nano-carriers, provides a new idea for developing multi-target, low environmental risk pesticide synergists, and has important significance for realizing pesticide reduction and resistance management. DETAILED DESCRIPTION

[0055] The present application will be further described below in combination with specific examples, but the examples do not limit the present application in any form. Unless otherwise specified, the reagents, methods and devices used in the present application are conventional reagents, methods and devices in the technical field.

[0056] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0057] Example 1 Preparation of azobenzene derivative Y-2

[0058]

[0059] A diazonium salt solution was prepared from 4-aminobenzoic acid (580 mg, 4.23 mmol), sodium nitrite (291.87 mg, 4.23 mmol) and concentrated hydrochloric acid (1 mL) in 6 mL water mixture, which was added to an ice-cold solution of calix[4]arene (424 mg, 1.0 mmol) and sodium acetate trihydrate (1.1 g, 8.08 mmol) in H2O / DMF (13 mL, 5:8, v / v) to give a red suspension. After stirring at room temperature for 2 h, the suspension was acidified with hydrochloric acid solution (1 mL, 37%), heated at 60 °C with stirring for 30 min, the reaction solution was filtered and the solid was washed with water and methanol to give the red product (yield: 90%). 1 H NMR (600 MHz, DMSO-d6) δ: 8.02 (d, J = 8.6 Hz, 8H), 7.82 (s, 8H), 7.81 (d, J = 8.5 Hz, 8H), 3.68 (s, 8H), this azobenzene derivative was named as Y-2.

[0060] Example 2 Preparation of azobenzene derivative Y-3

[0061]

[0062] A diazonium salt solution was prepared from 4-aminobenzoic acid (580 mg, 4.23 mmol), sodium nitrite (291.87 mg, 4.23 mmol) and concentrated hydrochloric acid (1 mL) in 6 mL water mixture, which was added to an ice-cold solution of calix[4]arene (424 mg, 1.0 mmol) and sodium acetate trihydrate (1.1 g, 8.08 mmol) in H2O / DMF (13 mL, 5:8, v / v) to give a red suspension. After stirring at room temperature for 2 h, the suspension was acidified with hydrochloric acid solution (1 mL, 37%), heated at 60 °C with stirring for 30 min, the reaction solution was filtered and the solid was washed with water and methanol to give the red product (yield: 90%). 1 H NMR (600 MHz, DMSO-d6) δ: 8.02 (d, J = 8.6 Hz, 8H), 7.82 (s, 8H), 7.81 (d, J = 8.5 Hz, 8H), 3.68 (s, 8H), this azobenzene derivative was named as Y-2.

[0063] Example 3 Preparation of azobenzene derivative Y-4

[0064]

[0065] Take 5-amino-2-chlorobenzoic acid 684.61 mg (3.99 mmol) dissolved in 3 mL H2O, add 1 mL concentrated HCl under cold bath condition, and slowly drop the pre-cooled NaNO2 aqueous solution after the temperature of the system is stable. Cup[4]arene 400 mg (0.94 mmol) and sodium acetate trihydrate 1.14 g (8.38 mmol) are dissolved in 10 mL MeOH:DMF (v:v = 5:8) and stirred under cold bath condition, then slowly drop the diazonium salt solution prepared before, stir for 30 min under ice bath, and stir for 4 h at room temperature. Adjust the pH of the reaction solution to 1, stir for 30 min under heating at 60 °C, filter while hot, and the product is a brown solid (yield: 80%). 1 H NMR (600 MHz, DMSO-d6) δ 8.23 (d, J = 2.1 Hz, 4H), 8.18 (d, J = 7.5 Hz, 4H), 8.09 (s, 4H), 7.96 (dd, J = 7.6, 2.1 Hz, 4H), 7.60 (s, 8H), 3.81 (s, 8H), which is named as Y-4.

[0066] Example 4 Preparation of azobenzene derivative Y-6

[0067]

[0068] Take p-aminobenzenesulfonic acid 2.60 g (15 mmol) and concentrated hydrochloric acid (3 mL, 37%) dissolved in 20 mL water, cool the solution to 2 °C under cold bath condition, slowly drop the pre-cooled NaNO2 aqueous solution (15 mL, 15 mmol), control the temperature of the system at 5 °C, and prepare a diazonium salt solution. Cup[4]arene 11.5 g (3.54 mmol) and anhydrous sodium acetate 3.69 g (Sodium acetate, abbreviated as SA, 45 mmol) are dissolved in 40 mL MeOH:DMF (v:v = 5:8) and stirred under cold bath condition, then slowly drop the diazonium salt solution prepared before, stir for 30 min under ice bath, and stir for 4 h at room temperature. Adjust the pH of the reaction solution to 1, stir for 30 min under heating at 60 °C, filter while hot, and wash the filter cake with water and methanol, and the product is a red solid (yield: 77%). 1 H NMR (600 MHz, DMSO-d6) δ 7.80 (s, 8H), 7.72 (d, J = 4.7 Hz, 8H), 7.70 (d, J = 8.6 Hz, 8H), 4.39 (s, 4H), which is named as Y-6.

[0069] Example 5 Preparation of azobenzene derivative Y-7

[0070]

[0071] Amino quaternary ammonium salt 374 mg (1.99 mmol) and concentrated hydrochloric acid (290 μί) were added to 1 mL of water, temperature controlled at 0-5 °C. 100 mg of sodium nitrite was dissolved in 1.16 mL of water, slowly added to the aqueous quaternary ammonium salt solution, then stirred at 0-5 °C for 30 min to prepare a diazonium salt solution. The resulting diazonium salt solution was slowly added to a solution of calix[4]arene (200 mg, 0.47 mmol) and sodium acetate trihydrate (374.6 mg, 2.75 mmol) in MeOH-DMF (3.75 mL, 5:8, V:v). After stirring at room temperature for 2.5 h, the solvent was removed by rotary evaporation. The residue was recrystallized from water / acetone, then filtered and dried to obtain a red solid. (Yield 75%) 1 H NMR (600 MHz, DMSO-d6) δ 8.08 (s, 8H), 7.85 (d, J = 8.5 Hz, 8H), 7.71 (s, 8H), 4.49 (s, 4H), 3.63 (s, 40H), this azobenzene derivative was named as Y-7.

[0072] Example 6 Preparation of azobenzene derivative Y-8

[0073]

[0074] Amino quaternary ammonium salt 374 mg (1.99 mmol) and concentrated hydrochloric acid (290 μί) were added to 1 mL of water, temperature controlled at 0-5 °C. 100 mg of sodium nitrite was dissolved in 1.16 mL of water, slowly added to the aqueous quaternary ammonium salt solution, then stirred at 0-5 °C for 30 min to prepare a diazonium salt solution. The resulting diazonium salt solution was slowly added to a solution of calix[4]arene (200 mg, 0.47 mmol) and sodium acetate trihydrate (374.6 mg, 2.75 mmol) in MeOH-DMF (3.75 mL, 5:8, V:v). After stirring at room temperature for 2.5 h, the solvent was removed by rotary evaporation. The residue was recrystallized from water / acetone, then filtered and dried to obtain a red solid. (Yield 75%) 1H NMR (600 MHz, DMSO-d6) δ 8.09 (s, 4H), 8.07 (dd, J = 7.4, 5.5 Hz, 4H), 7.92 (dd, J = 27.1, 7.4 Hz, 4H), 7.85 (t, J = 7.5 Hz, 4H), 7.81 - 7.73 (m, 4H), 7.69 - 7.64 (m, 4H), 7.57 (dd, J = 7.5, 4.2 Hz, 4H), 7.47 (s, 8H), 3.81 (d, J = 1.6 Hz, 8H), the azobenzenes derivative was named as Y-8.

[0075] Example 7 Preparation of azobenzenes derivative Y-10

[0076]

[0077] Y-2 was synthesized according to Example 2, Y-2 (200 mg, 0.2 mmol) was dissolved in 2 mL DMF, HATU (38.1 mg, 0.1 mmol) was added under ice bath condition, DIPEA (25.9 mg, 0.2 mmol), hydrochloride-D-mannosamine (21.56 mg, 0.1 mmol) were added in turn every 20 min, the temperature was raised to room temperature and stirred overnight, rotary evaporation to get red solid. (Yield 45%). 1 H NMR (600 MHz, DMSO-d6) δ 8.35 - 8.30 (m, 5H), 8.14 - 8.09 (m, 6H), 8.09 (d, J = 2.0 Hz, 7H), 7.61 (d, J = 0.9 Hz, 7H), 6.58 (d, J = 3.1 Hz, 1H), 4.94 (d, J = 5.7 Hz, 1H), 4.88 (d, J = 5.7 Hz, 1H), 4.48 (s, OH), 4.48 (d, J = 9.0 Hz, OH), 4.20 (dd, J = 4.4, 3.1 Hz, 1H), 4.01 (dtd, J = 8.4, 6.1, 2.4 Hz, 1H), 3.81 (q, J = 0.7 Hz, 7H), 3.73 - 3.66 (m, 2H), 3.63 (ddd, J = 12.1, 4.5, 3.0 Hz, 1H), 3.23 -.17 (m, 1H), 3.11 (tdd, J = 8.4, 5.7, 3.7 Hz, 1H), the azobenzenes derivative was named as Y-10.

[0078] Example 8 Preparation of isoprothiolane-based azobenzenes calix[4]arene complex

[0079] The azobenzene calix[4]arene derivative prepared in Example 1-7 was dissolved in 500 mL of dimethyl sulfoxide, and the guest molecule bithionol was dissolved in the same solvent. The two solutions were mixed and stirred at room temperature for 24 hours, and dried in vacuum to obtain the corresponding host-guest complex.

[0080] Effect test:

[0081] The following tests illustrate the fungicidal effect of the above-prepared formulations of Example 8 (bithionol@Y-2, bithionol@Y-3, bithionol@Y-4, bithionol@Y-6, bithionol@Y-7, bithionol@Y-8, bithionol@Y-10) on Xanthomonas campestris (Xac), Pseudomonas syringae pv. lachrymans (Psl) and Clavibacter michiganensis (Cmm).

[0082] In all the following tests, the concentration (or amount) refers to the concentration (or amount) of the active substance pesticide.

[0083] The comparative formulations used in the following tests are:

[0084] The bithionol@Y-1 complex was prepared by the following method: Y-2 and bithionol (1:1 by mole) were used to prepare bithionol@Y-2 according to the preparation method of Example 8. Bithionol@Y-3, bithionol@Y-4, bithionol@Y-6, bithionol@Y-7, bithionol@Y-8 and bithionol@Y-10 were prepared in the same way.

[0085] 1. In vitro activity of bithionol@azobenzene calix[4]arene complex on plant pathogenic bacteria

[0086] 1) The test was based on the turbidity method, with improvements. The azobenzene calix[4]arene pesticide complex was accurately weighed using an electronic balance, and the complex was first diluted to a 10,000 μm / L mother liquor. The prepared solution was added to 5 mL of nutrient broth, followed by the addition of 40 μL of bacterial suspension (OD 595nm = 0.6), and it was placed in a shaker (180 rpm, 28°C) for 48 h until the relevant pathogenic bacteria (positive control) grew to the logarithmic phase. 2 mL was taken from each sample, and the UV spectrophotometer gave the corresponding turbidity at 595 nm. The inhibition rate of each agent at different concentrations on the growth of pathogenic bacteria was calculated according to the following formula. The test bacteria were Xanthomonas campestris, Clavibacter michiganensis and Pseudomonas syringae pv. lachrymans.

[0087] NB liquid medium composition: 5.0 g of bacteriological peptone, 1.0 g of yeast powder, 3.0 g of beef extract and 10.0 g of glucose were dissolved in 1.0 L of deionized water, and the pH was adjusted to 7.2.

[0088] T = OD 有菌 - OD无菌

[0089] I = (C - T) / C x 100%

[0090] T: turbidity correction value;

[0091] C: correction turbidity value of solvent control three repeated determination.

[0092] The effects are shown in Table 1.

[0093] Table 1 In vitro antibacterial activity results of BTH@ azobenzo cup[4] arene

[0094]

[0095] As shown in Table 1, BTH@ azobenzo cup[4] arene has different degrees of inhibition on Xanthomonas campestris pv. citri, Pseudomonas syringae pv. lachrymans and Xanthomonas campestris pv. vesicatoria, especially BTH@ Y-2 has excellent inhibition on the three different bacteria, with inhibition effect close to 100%.

[0096] 2) In vitro antibacterial gradient test of some BTH@ azobenzo cup[4] arene complexes

[0097] The test was carried out by plate growth-turbidity method. BTH and BTH@ azobenzo cup[4] arene complex were prepared into 10000 μm / L stock solution for standby. The activated pathogenic bacteria single colony was picked into 50 mL NB liquid medium, which was placed in a shaker (180 rpm, 28°C) for 24 h to obtain bacterial suspension. The suspension was diluted to 1 x 10 8

[0098] The 10000 μm / L stock solution was diluted by gradient, and the drug solution was added into 50 mL melted NB solid medium, mixed uniformly, and then poured into a culture dish with a diameter of 9 cm. The medium was evenly divided into 3 parts to prepare NB plates containing drug solution. After the plates were solidified, 100 μL of bacterial suspension was evenly coated on the entire plate by coating method, and the plate was placed in a 25°C incubator for culture. DMSO was used as negative control, and sterile water was used as blank control. Each sample was repeated 3 times, and all operations were carried out on a sterile operation table. After the culture was completed, 10 mL of sterile water was used to wash the colonies and mix them into a suspension. The absorbance value was measured at 595 nm on a UV spectrophotometer.

[0099] The inhibition rate of each complex on the growth of pathogenic bacteria was calculated according to the following formula, and the data was processed by Spss to calculate the independent regression equation (y = b + ax) of the complex, the correlation coefficient (R), the inhibition concentration (EC 50 ) and the synergistic coefficient (SR) ​

[0100]

[0101] Table 2 EC of Bupirimate@ azobenzoate calix[4]arene complex on three plant pathogenic bacteria 50 Value

[0102]

[0103] Table 3 Synergistic coefficient of Bupirimate@ azobenzoate calix[4]arene complex on three plant pathogenic bacteria

[0104]

[0105] From Tables 2-3, it can be seen that the determined Bupirimate@ azobenzoate calix[4]arene has different degrees of synergistic effect on at least one of Xanthomonas axonopodis pv. citri, Pseudomonas syringae pv. lachrymans and Xanthomonas campestris pv. vesicatoria, and can be used as a synergist to promote the bactericidal effect of the insecticide Bupirimate on the bacteria. Among them, the supramolecular complex Bupirimate@ Y-2 shows a breakthrough control effect on both gram-negative and gram-positive plant pathogenic bacteria. For Xanthomonas axonopodis pv. citri (Xac), the EC value of the complex is 14.15±1.15 μg / mL, which is 2.13 times the synergistic coefficient (SR) of free Bupirimate (30.10±2.80 μg / mL); for Pseudomonas syringae pv. lachrymans (Psl), the EC value is 5.03±0.15 μg / mL (SR=7.59), which is significantly better than the control agent Bupirimate (EC = 38.16±1.04 μg / mL); and in the model of Xanthomonas campestris pv. vesicatoria (Cmm), the EC value is reduced to 8.19±0.32 μg / mL (SR=3.44), which is more than 3.5 times the activity of the traditional copper preparation. It can be seen that the synergistic effect of Bupirimate@ Y-2 complex on Xanthomonas axonopodis pv. citri (Xac), Pseudomonas syringae pv. lachrymans (Psl) and Xanthomonas campestris pv. vesicatoria (Cmm) is the strongest, and it shows excellent synergistic effect. 50 50 50 50

[0106] 2. Pot experiment of the bactericidal activity of Bupirimate@ Y-2 complex against Pseudomonas syringae pv. lachrymans

[0107] A pot experiment was conducted, and the seeds of cucumber were selected for planting in the seedling pots after being soaked for 24 h. The seedlings were used for the experiment when they grew to 2-3 true leaf stage. The control agent was a commercially available agricultural bactericide Bupirimate (20% wettable powder), and DMSO was used as a blank control. The complex and the agent were prepared into a concentration of 200 μg / mL. 10 mL of Psl suspension (OD 595 ​​​​The cucumber seedlings were inoculated with the compound and the fungicide at a concentration of 200 μg / mL, 10 times of parallel, 3 times of repetition, and the seedlings were kept moist for 48 hours after inoculation. The control effect was investigated 14 days after inoculation.

[0108] The grading standard of cucumber bacterial angular leaf spot pathogen is as follows: 0 grade: no disease on the whole leaf; 1 grade: a few disease spots, accounting for less than 1 / 5 of the leaf area; 2 grade: a few small spots, accounting for 1 / 5-1 / 3 of the leaf area; 3 grade: many disease spots, accounting for 1 / 3-2 / 3 of the leaf area; 4 grade: many medium-sized disease spots, accounting for more than 2 / 3 of the leaf area, with moderate bacterial overflow; 5 grade: whole leaf disease, with much bacterial overflow, and some disease spots are dry and form perforations.

[0109] Disease index = ∑(number of leaves at each grade × corresponding grade value) / (total number of leaves surveyed × 5) × 100

[0110] Control effect (%) = (disease index of control - disease index of treatment) / disease index of control × 100

[0111] Table 4 Control results of folpet@Y-2 supramolecular complex on Psl at 200 μg / mL

[0112]

[0113] Note: P represents the protective test group, and C represents the therapeutic test group.

[0114] As can be seen from Table 4, whether in the protective test or in the therapeutic test, folpet@Y-2 supramolecular complex has the best control effect, indicating that it can be used as a synergist of fungicides.

[0115] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application should be equivalent replacement methods, and are all included in the protection scope of the present application.

Claims

1. A class of azobenzene calix[4]arene derivatives or an agronomically acceptable salt thereof, characterized in that, The azobenzene calix[4]arene derivative or its agriculturally acceptable salt has a structure as shown in formula (I): In formula (I), the R 1 is selected from -COOH, -SO3H, -SO2NH2, or -COOH is unsubstituted or substituted by a substituent R 3 , the R 3 is selected from The X - represents an anion; the R 2 is selected from hydrogen, C 1～6 alkyl, haloC 1～6 alkyl or halogen.

2. The azobenzene-based calix[4]arene derivative or an agriculturally acceptable salt thereof according to claim 1, wherein said R 2 selected from hydrogen, C 1～3 alkyl, haloC 1～3 alkyl or halo.

3. The azobenzene-based calix[4]arene derivative or an agriculturally acceptable salt thereof according to claim 1, wherein The halogen is selected from chlorine, bromine, fluorine or iodine.

4. The azobenzene-based calix[4]arene derivative or an agriculturally acceptable salt thereof according to claim 1, wherein The X represents halogen.

5. A process for producing the azobenzene-based calix[4]arene derivative or the agriculturally acceptable salt thereof according to any one of claims 1 to 4, characterized by, The method comprises the following steps: S1. preparing a diazonium salt solution with compound 1, adding a solvent solution containing compound 2, sodium acetate or its hydrate, and performing a reaction to obtain the target compound I-1; S2. When R 1 is selected from -COOH, and is substituted with R 3 , the compound I-1 obtained in S1 and D-mannosamine hydrochloride are used as the raw materials, and the reaction is performed under the conditions of a solvent, a condensing agent, and an organic base to obtain the target compound I-2:

6. The preparation method according to claim 5, characterized in that, The diazonium salt solution is prepared by the following steps: mixing compound 2, sodium nitrite, hydrochloric acid and a solvent under ice bath conditions, and performing a reaction to obtain the diazonium salt solution.

7. Use of the azobenzene calix[4]arene derivative or its agriculturally acceptable salt as claimed in any one of claims 1 to 4 as a pesticide synergist.

8. An azobenzene-based calix[4]arene complex, characterized by The azobenzene calix[4]arene complex takes the azobenzene calix[4]arene derivative or its agriculturally acceptable salt as claimed in any one of claims 1 to 4 as a host compound, and a pesticide as a guest compound, and the two are combined to obtain the azobenzene calix[4]arene complex.

9. The azobenzene-based calix[4]arene complex according to claim 8, wherein The pesticide is a fungicide.

10. A pesticidal composition, characterized by, The pesticide composition comprises the azobenzene calix[4]arene complex as claimed in claim 8 or 9 and an agriculturally acceptable adjuvant.

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