Oxime compounds for degradation of organophosphorus pesticides and preparation method and application thereof

Abstract

The application discloses an oxime compound for degradation of organophosphorus pesticides and a preparation method and application thereof, and belongs to the technical field of organophosphorus pesticide detection and degradation. The long conjugated aryl hydrophobic group is introduced into the oxime compound, and the combination efficiency and degradation performance of the oxime compound and the pesticide can be significantly improved under the catalysis of a micelle system. Meanwhile, the intramolecular push-pull electron effect of the target oxime compound is accurately controlled, the aryl conjugated pi system is greatly extended, the fluorescence emission wavelength of the oxime compound is red-shifted, a high-sensitivity fluorescence detection method is established to make up for the deficiency of traditional ultraviolet analysis. Meanwhile, the solubility and stability of the oxime compound are significantly improved through electron effect optimization, and the targeting degradation ability and in-vivo biological activity of the oxime compound are significantly improved, so that a reliable scheme is provided for detection and effective degradation of organophosphorus compounds.

Description

Technical Field

[0001] This invention relates to the field of organophosphorus pesticide detection and degradation technology. More specifically, this invention relates to an oxime compound for the degradation of organophosphorus pesticides, its preparation method, and its application. Background Technology

[0002] Organophosphorus pesticides (OPs) are chemically stable and have long half-lives, making them highly likely to remain on the surface of agricultural products and spread through soil infiltration and water flow, posing a continuous threat to the ecological environment and agricultural product safety.

[0003] Currently, commonly used methods for detecting organophosphorus pesticides (OPs) mainly include gas chromatography (GC), high-performance liquid chromatography (HPLC), or liquid chromatography-mass spectrometry (LC-MS). However, all of these methods require samples to be sent to the laboratory for pretreatment, which is complex and time-consuming, making on-site detection impossible. Regarding OOPs degradation, researchers have developed various composite materials, modified titanium dioxide composite catalysts, hydrolytic nanozymes, and photocatalytic degradation methods. Li Ying et al., in their paper "A New Technology for Visible Light Catalytic Degradation of Trace Organophosphorus Pesticides in Aquatic Environments (CN117466373 [P].2024)," prepared nitrogen carbide materials using high-temperature pyrolysis and grew zirconium-based MOFs on their surface as a highly efficient composite photocatalyst for visible light catalytic degradation of trace OOPs in the aquatic environment. Peng Yinan et al., in their paper "Bacillus subtilis with High Efficiency Degradation of Organophosphorus Pesticides and its Preparation Method (CN110591941 [P].2019)," cultured and selected strains with strong degradation capabilities from Bacillus subtilis, and obtained the desired Bacillus subtilis through mutagenesis for efficient OOPs degradation.

[0004] The neurotoxicity of OPs stems from the covalent binding of their phosphate ester groups to serine residues at the active site of acetylcholinesterase (AChE), leading to the accumulation of acetylcholine and resulting in poisoning. Anal. Methods ,2021, 13, 4390-4428; Int. J. Mol. Sci .,2023, 24, 14213). Current research mainly focuses on the development of detection and degradation technologies, among which nucleophilic degradation reagents (such as peroxides, hypochlorites, etc.) have corrosive and environmental toxicity issues. Tetrahedron Lett (2004, 45, 9103-9105). In contrast, oxime compounds have become a research hotspot due to their advantages such as hypernucleophilicity and non-corrosiveness.

[0005] As α-effect hypernucleophiles, oxime derivatives (such as 2-pyridinecarboxaldehyde oxime iodomethane (2-PAM); salicylaldehyde oxime, etc.) can effectively activate phosphorylated AchE through nucleophilic substitution reactions with OPs via the oxime group. J. Phys. Chem. B,2010,114, 16759-16765). However, the low water solubility of reactants during OPs degradation leads to PO bond hydrolysis depending on a highly efficient catalytic support ( Colloids and Surfaces A: Physicochem. Eng. Aspects, 2008, 315, 103-109. Surfactant micelles are commonly used as reaction media, but their catalytic efficiency is significantly affected by the lipophilicity of pesticide substrates. For example, ethyl parathion has a high hydrophilicity, resulting in low solubility and inclusion rates in the micelle phase, making it difficult to degrade. Langmuir (2001, 17, 3819-3828). Hydrophobic degradative agents can significantly improve degradation efficiency by binding with pesticides at the micelle interface.

[0006] While existing oxime derivatives can effectively degrade organophosphorus pesticides and their structural analogs, significant technical bottlenecks remain in practical applications: key issues such as insufficient hydrolysis efficiency and reactivity, potential secondary pollution, and lack of real-time monitoring capabilities urgently need to be addressed.

[0007] (1) Existing technologies improve degradation efficiency and reactivity by loading oxime molecules (or hydroxamic acid ions) onto functional polymers or forming comicelle systems with inert surfactants. J Mol Liq (2017, 243, 178-186), but this strategy has significant limitations: the experiment requires excessive addition of the carrier to ensure effective binding of pesticides and degrading agents, leading to operational complexity. Simultaneously, multiple parameters need to be monitored, including the degree of deprotonation of oxime molecules, the degree of pesticide micellization, carrier concentration, critical micelle concentration, reaction kinetics, pH effect, metal ion catalytic interference, and local concentration at the micelle interface. Furthermore, the long degradation cycle and poor detection timeliness severely restrict the practical application of organophosphorus pesticide degradation.

[0008] (2) Studies have shown that the degradation rate of OPs by oxime derivatives is significantly positively correlated with the pH value of the system, and the degradation kinetics can be significantly enhanced in an alkaline environment (pH 9.0-12.4). J. Org. Chem .,1997, 62, 2198-2204;1978, 43(14), 2816-2821). Therefore, strong bases such as NaOH and KOH are often added to maintain the alkalinity of the system in experiments. However, although the introduction of strong bases can accelerate the degradation reaction, it will cause serious secondary pollution.

[0009] (3) Current methods for detecting phenolic anions, degradation products of OPs, mainly rely on ultraviolet spectroscopy. J. Org. ChemHowever, this method has obvious limitations in trace detection: the insufficient sensitivity leads to a high detection limit, making it difficult to effectively monitor low-concentration degradation products. More critically, the degradation agent concentration in actual sample systems is usually much higher than that of the pesticide substrate, and the UV spectrum signal is distorted by the strong interference of the high-concentration degradation agent, severely affecting the quantitative accuracy of the degradation reaction.

[0010] Organophosphorus compounds in environmental actual samples usually exist at trace levels, accompanied by a large number of structural analogues and homologues, resulting in complex system components and significant interference. Therefore, developing an organophosphorus pesticide degradation reagent with high sensitivity and selectivity, convenient operation, easy monitoring of degradation products, and efficient degradation under physiological to weak alkaline conditions (pH 7.5-9.0) has become a key path to solving the above technical bottlenecks. SUMMARY

[0011] It is an object of the present application to solve at least the above problems and / or deficiencies, and to provide at least the advantages described hereinafter.

[0012] It is another object of the present application to provide a series of oxime compounds for degradation of organophosphorus pesticides, which solve the technical problems of low catalytic efficiency, limited detection means, and poor environmental compatibility in the prior art. By introducing a long conjugated aromatic hydrophobic group, the combination efficiency and degradation performance with pesticides can be significantly improved under the catalysis of a micellar system.

[0013] It is still another object of the present application to provide a method for preparing oxime compounds for degradation of organophosphorus pesticides, which has readily available raw materials, simple operation, and high yield of target products.

[0014] It is still another object of the present application to provide oxime compounds for degradation of organophosphorus pesticides, which can be used for detection and degradation of organophosphorus compounds, and more importantly, organophosphorus pesticides in environmental media, including water bodies, atmosphere, soil, pesticide production workshops, etc.; which can be used for preparing imaging kits, test papers, colorimetric cards or test cards, portable detection devices for detecting organophosphorus pesticides, synergists for use with other compounds, remediation agents for environmental media contaminated with organophosphorus pesticides, and naked-eye or fluorescent detection for in-situ identification and degradation of organophosphorus pesticides.

[0015] To achieve these objects and other advantages in accordance with the present application, a kind of oxime compound for degradation of organophosphorus pesticides is provided, which is as follows formula (I) or (II) compound or its acceptable salt, diastereoisomer, tautomer, hydrate or solvate:

[0016] (I);

[0017] (II);

[0018] wherein, in formula I, n is selected from any integer from 0 to 6, X is selected from O or S or Se, R1 represents mono, di, tri, tetra or penta substitution, the substituents being -H, -OH, -OC m H 2m+1 , m = 1-12, -NH2, -NH-R, R being an alkyl group, -NH-CO-R4, R4 being an alkyl group, -NO2, -CF3, -CCl3, -CN, -N + R5, R5 being an alkyl, alkenyl, alkynyl, cycloalkyl or aryl group, and -SO3H, alone or in combination;

[0019] wherein, in formula II, n1 is selected from any integer from 0 to 6, X1 is selected from O or S or Se, R2 represents mono, di, tri, tetra or penta substitution, the substituents being -H, -OH, -OC m H 2m+1 , m = 1-12, -NH2, -NH-R, R being an alkyl group, -NH-CO-R4, R4 being an alkyl group, -NO2, -CF3, -CCl3, -CN, -N + R5, R5 being an alkyl, alkenyl, alkynyl, cycloalkyl or aryl group, and -SO3H, alone or in combination; R3 being H or C m H 2m+1 , m = 1-12. Y is independently selected from halide ions, including chloride, iodide, bromide.

[0020] Preferably, the oxime compound used for degradation of organophosphorus pesticides is any one of the following compounds:

[0021] , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

[0022] The object of the present application can be further achieved by a method for preparing the oxime compound for degradation of organophosphorus pesticides, comprising the following steps:

[0023] S1, using 5-bromopyridine-2-carboxaldehyde as raw material, refluxing with ethylene glycol in the presence of p-toluenesulfonic acid monohydrate to generate the following formula (III) intermediate;

[0024] S2, using bromobiphenyl compounds as raw material, under the protection of nitrogen, in the presence of a catalyst and a base, reacting with pinacol diboron to generate biphenyl borate compounds;

[0025] S3, the intermediate of formula (III) and biphenyl borate compounds are subjected to multi-step reaction to obtain the final compound;

[0026] (III).

[0027] Preferably, in step S1, the mixing ratio of 5-bromopyridine-2-carboxaldehyde, p-toluenesulfonic acid monohydrate and ethylene glycol is 10 mmol: 1 mmol: 4 mL.

[0028] Preferably, in step S2, the catalyst is [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, and the molar ratio of the catalyst to bromobiphenyl compounds is 1:10.

[0029] Preferably, the base is potassium acetate, and the molar ratio of the base to bromobiphenyl compounds is 5:2.

[0030] The object of the present application can be further achieved by the application of the oxime compound for degradation of organophosphorus pesticides in the detection and degradation of organophosphorus pesticides. ​​​​​​​​​​​​​​​​​​​​​​

[0031] The application can also be further used for the preparation of an imaging kit, test paper, colorimetric card or detection card, portable detection device, synergist for use in combination with other compounds, remediation agent for an environment medium contaminated with organophosphorus pesticides.

[0032] The application at least includes the following advantages:

[0033] First, the oxime compound for organophosphorus pesticide degradation of the application significantly enhances the liposolubility of the target compound by constructing an aryl hydrophobic structure with π-π conjugation effect. This design not only optimizes the adsorption capacity of the oxime molecule on the micelle interface, but also significantly improves the enrichment concentration of the pesticide substrate on the micelle surface through hydrophobic-hydrophobic interaction, thereby increasing the degradation reaction rate constant to 4-5 times that of traditional degradation agents.

[0034] Second, the oxime compound for organophosphorus pesticide degradation of the application uses a synergistic modification strategy of OCH3 (electron-donating group) and NO2 / CF3 (electron-withdrawing group), so that the electron cloud density of the conjugated aromatic ring presents a significant difference. This design makes the maximum emission wavelength of the target derivative red-shifted (more than 50 nm), not only greatly improving the fluorescence quantum yield, but also reducing the activation energy of the degradation reaction through the ICT (intramolecular charge transfer) effect, realizing high-sensitivity fluorescence detection, and providing a basis for the development of naked-eye colorimetric recognition, making up for the shortcomings of traditional ultraviolet analysis.

[0035] Third, the high specificity of the oxime compound for organophosphorus pesticide degradation of the application promotes its high activity in the physiological to weak alkaline range of pH=7.5-9.0. In this pH range, the degradation ability of the new derivative is significantly better than that of traditional degradation agents or hydrolytic enzymes, and effectively avoids the secondary pollution problem caused by strong alkali.

[0036] Other advantages, objects and features of the application will be partly embodied by the following description, and will be partly understood by those skilled in the art through research and practice of the application. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 The nuclear magnetic hydrogen spectrum of the compound BTFM-Py-OX prepared in Example 1 of the application;

[0038] Figure 2 The nuclear magnetic hydrogen spectrum of the compound BTFM-Py-M-OX prepared in Example 1 of the application;

[0039] Figure 3 The nuclear magnetic carbon spectrum of the compound BTFM-Py-M-OX prepared in Example 1 of the application;

[0040] Figure 4 NMR of hydrogen spectrum of compound BMO-Py-OX prepared in Example 2 of the present application;

[0041] Figure 5 NMR of carbon spectrum of compound BMO-Py-OX prepared in Example 2 of the present application;

[0042] Figure 6 Mass spectrum of product of degradation of phosalone by BTFM-Py-OX in Example 6 of the present application (instrument not calibrated);

[0043] Figure 7 Mass spectrum of product of degradation of phosalone by BTFM-Py-OX in Example 6 of the present application (overall);

[0044] Figure 8 Mass spectrum of product of degradation of phosalone by BTFM-Py-OX in Example 6 of the present application (partial);

[0045] Figure 9 UV spectrum display of in-situ reaction of BTFM-Py-M-OX with organophosphorus pesticides in Example 7 of the present application;

[0046] Figure 10 Fluorescence titration experimental results of in-situ reaction of BTFM-Py-M-OX with organophosphorus pesticides in Example 7 of the present application;

[0047] Figure 11 Elemental composition analysis of fluorescence in-situ titration solution of BTFM-Py-OX with organophosphorus pesticides in Example 7 of the present application;

[0048] Figure 12 Elemental composition analysis of fluorescence in-situ titration solution of BTFM-Py-M-OX with organophosphorus pesticides in Example 7 of the present application. DETAILED DESCRIPTION

[0049] The present application will be further described in conjunction with the accompanying drawings, so that those skilled in the art can implement the present application according to the description and drawings.

[0050] It should be understood that the terms such as "have", "contain" and "include" used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0051] It should be noted that the experimental methods in the following embodiments are all conventional methods, and the reagents and materials are commercially available unless otherwise specified.

[0052] Example 1

[0053] An ortho-pyridine oxime derivative for degrading organophosphorus pesticides, which has the following structure:

[0054] or

[0055] The synthetic route is as follows:

[0056]

[0057]

[0058] The specific synthesis steps are as follows:

[0059] Synthesis of compound 1: 4'-Bromo-[1,1'-biphenyl]-4-carboxaldehyde (2.60 g, 10 mmol) was dissolved in anhydrous 1,4-dioxane (15 mL) under nitrogen protection, and then pinacol diborane (3.81 g, 15 mmol), [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride (0.73 g, 1 mmol) and potassium acetate (2.45 g, 25 mmol) were added in sequence, and stirred under reflux. The reaction was monitored by LC-MS, and the starting material was completely reacted after 7.5 h. After stopping the reaction, the product was adsorbed and filtered with diatomite, the filtrate was rotary evaporated, the crude product was dissolved in dichloromethane (20 mL), washed with water three times, each time with 20 mL of water, dried with anhydrous sodium sulfate, and the organic phase was combined and rotary evaporated. Purification was performed by flash column chromatography (petroleum ether / ethyl acetate = 10 / 1, v / v) to obtain yellowish solid 1 (2.07 g, yield: 67.2%). HRMS calcd for C 19 H 20 BO3 - , 307.1584 [M-H] - ; found,307.1576.

[0060] Synthesis of compound 2: 5-Bromopyridine-2-carboxaldehyde (3.7 g, 20 mmol) was dissolved in an appropriate amount of toluene (35 mL), and an excess of ethylene glycol (8 mL) and p-toluenesulfonic acid monohydrate (0.38 g, 2 mmol) were added. After stirring thoroughly, the reaction was carried out under reflux. The reaction was stopped after 2.5 h. The toluene was rotary evaporated, ethyl acetate (40 mL) was added, and the mixture was washed with water three times, each time with 30 mL of water. The organic phase was combined and dried, and the ethyl acetate was rotary evaporated. Purification was performed by flash column chromatography (petroleum ether / ethyl acetate = 4 / 1, v / v) to obtain white solid 2 (3.93 g, 85.8%). HRMS calcd for C8H8BrNO2 + , 228.9738[M] + ; found, 228.9742。

[0061] Synthesis of compound 3: Compound 2 (1.15 g, 5 mmol) was dissolved in anhydrous 1,4-dioxane (15 mL) under nitrogen protection, compound 1 (1.54 g, 5 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (0.37 g, 0.5 mmol) and potassium acetate (1.23 g, 12.5 mmol) were added successively, and the reaction was carried out at 105 °C. The reaction was monitored by LC-MS, and the starting material was completely consumed after 5 h. After stopping the reaction, the filtrate was adsorbed on diatomite and dried by rotary evaporation. The crude product was dissolved in dichloromethane (25 mL), washed with water three times (15 mL each time), dried over anhydrous sodium sulfate, and the organic phase was combined and rotary evaporated. Purification by flash column chromatography (petroleum ether / ethyl acetate = 2 / 1, v / v) gave compound 3 as a nearly white solid (0.88 g, yield: 53.4%). 1 H NMR (300 MHz, DMSO-d6) δ 10.07 (s, 1H), 8.95 (s, 1H), 8.23 (d, J = 8.1 Hz, 1H), 8.01 (m, 4H), 7.92 (s, 4H), 7.63 (d, J = 8.1 Hz, 1H), 5.80 (s, 1H), 4.13 (m, 2H), 4.03 (m, 2H). HRMS calcd for C 21 H 18 NO3 + , 332.1287[M+1] + ; found, 332.1292.

[0062] Synthesis of compound 4: Compound 3 (0.66 g, 2 mmol) was dissolved in anhydrous 1,4-dioxane (10 mL) under nitrogen protection, and 3,5-bistrifluoromethylacetophenone (0.77 g, 3 mmol) and piperidine (0.43 g, 5 mmol) were added. The reaction was carried out at 105 °C, and the reaction was monitored by LC-MS. The reaction was stopped after 24 h. After removing the solvent, an appropriate amount of ethyl acetate (15 mL) was added, and the mixture was washed with water three times (10 mL each time). The organic phase was combined and dried, and compound 4 was separated by flash column chromatography (petroleum ether / ethyl acetate = 1 / 2, v / v) to give a yellowish solid (0.79 g, yield: 70.1%). 1H NMR (300 MHz, DMSO-d6) δ 8.94 (s, 1H), 8.78 (s,2H), 8.44 (s, 1H), 8.20 (m, 2H), 8.10 (d, J = 8.0 Hz, 2H), 7.92 (m,7H), 7.63(d, J = 8.2 Hz, 1H), 5.80 (s, 1H), 4.13 (m, 2H), 4.03 (m, 2H). HRMS calcd for C 31 H 22 F6NO3 + , 570.1504[M+1] + ; found, 570.1510.

[0063] Synthesis of compound 5: Compound 4 (0.29 g, 0.5 mmol) was dissolved in anhydrous dichloromethane (5 mL), 1 M hydrochloric acid in dioxane (6 mL) was added, and the reaction was stirred at room temperature. After 1 h, the starting material was consumed, and the solvent was removed by rotary evaporation. Compound 5 was isolated as a light yellow solid (0.24 g, yield: 92.4%) by flash column chromatography (petroleum ether / ethyl acetate = 1 / 1, v / v). 1 H NMR (300 MHz, DMSO-d6) δ 10.05 (s, 1H), 9.25 (s, 1H), 8.78 (s, 2H), 8.43 (d, J =8.7 Hz, 2H), 8.21 (d, J = 15.6 Hz, 1H), 8.12 (d, J = 8.1 Hz, 2H), 8.02 (dd, J=15.1, 5.8 Hz, 9H), 7.92 (d, J = 7.7 Hz, 3H).HRMS cal for C 29 H 18 F6NO2 + ,526.1242[M+1] + ; found, 526.1250.

[0064] Synthesis of compound BTFM-Py-OX: Compound 5 (0.15 g, 0.29 mmol) was dissolved in ethanol (10 mL) under nitrogen protection, sodium carbonate aqueous solution (1.5 mol / L, 3 mL) was added, and excess hydroxylamine hydrochloride (0.30 g, 4.35 mmol) was added under stirring. The reaction was carried out at room temperature. After 2 h, the raw material was consumed, ethanol was removed by rotary evaporation, and then an appropriate amount of dichloromethane (15 mL) was added. The organic phase was washed with water three times, each time with 10 mL of water. The organic phase was combined and dried. The solvent was removed by rotary evaporation, and column chromatography (dichloromethane / methanol = 10 / 1, v / v) was used to separate the product to obtain a light yellow solid BTFM-Py-OX (0.14 g, yield: 89.0%). 1 H NMR (300 MHz, DMSO-d6) δ 11.76 (s, 1H), 8.99 (s, 1H), 8.78 (s, 2H), 8.45 (s, 1H), 8.15 (m, 5H), 7.94(m, 8H).HRMS calcdfor C 29 H 19 F6N2O2 + , 541.1351[M+1] + ; found, 541.1357.

[0065] wherein the hydrogen spectrum of compound BTFM-Py-OX is shown in Figure 1 .

[0066] Synthesis of compound BTFM-Py-M-OX: Compound BTFM-Py-OX (0.10 g, 0.19 mmol) was dissolved in chromatographic acetonitrile (8 mL) under nitrogen protection, and iodomethane (0.04 g, 0.29 mmol) was added. The reaction was carried out at reflux. After 6.5 h, the raw material was consumed, acetonitrile was removed by rotary evaporation, and then an appropriate amount of dichloromethane (10 mL) was added. The organic phase was washed with water three times, each time with 10 mL of water. The organic phase was combined and dried. Dichloromethane was removed by rotary evaporation, and column chromatography (dichloromethane / methanol / ammonia water = 90 / 9 / 1, v / v) was used to separate the product to obtain a light yellow solid BTFM-Py-M-OX (0.09 g, yield: 87.7%). 1 H NMR (300 MHz, DMSO-d6) δ 13.18 (s, 1H), 9.51 (s,1H), 8.93 (d, J = 8.5 Hz, 1H), 8.76 (d, J = 11.7 Hz, 3H), 8.44 (d, J =9.1 Hz,2H), 8.15 (m, 7H), 7.95 (d, J = 8.9 Hz, 3H), 4.47 (s, 3H). 13C NMR (75 MHz, DMSO-d6) δ 187.10, 146.17, 145.89, 144.95, 142.03, 141.36, 139.94, 138.14,134.70, 132.77,131.16, 130.67, 129.53, 128.30, 127.68,125.30, 121.79, 46.93.HRMS calcd for C 30 H 21 F6N2O2 + , 555.1502[M] + ; found, 555.1512.

[0067] The 1H NMR spectrum of compound BTFM-Py-M-OX is as follows: Figure 2 As shown, the carbon NMR spectrum is as follows: Figure 3 As shown.

[0068] Example 2

[0069] An o-pyridine oxime derivative for degrading organophosphorus pesticides has the following structure:

[0070] or

[0071] The synthesis route is as follows:

[0072]

[0073] The specific synthesis steps are as follows:

[0074] Synthesis of Compound 6: Under nitrogen protection, Compound 3 (0.87 g, 2.63 mmol) was dissolved in ethanol (12 mL), followed by the addition of 3,5-dimethoxyacetophenone (0.71 g, 3.95 mmol) and an aqueous solution of sodium hydroxide (1.0 mol / L, 2.5 mL). The reaction was carried out at room temperature, monitored by LC-MS, and stopped after 7 h. After removing the ethanol by rotation, an appropriate amount of dichloromethane (10 mL) was added, and the mixture was washed three times with 10 mL of water each time. The organic phases were combined and dried, and separated by column chromatography (petroleum ether / ethyl acetate = 1 / 1, v / v) to give a nearly white solid 6 (0.79 g, yield: 70.1%). 1H NMR (300 MHz, DMSO-d6) δ 8.95 (s, 1H), 8.21 (d, J = 6.6 Hz, 1H), 8.03 (m, 2H), 7.98 – 7.79(m, 8H), 7.63 (d, J = 8.0Hz, 1H), 7.30 (s, 2H), 6.81 (s, 1H), 5.79 (s, 1H), 4.13 (m, 2H), 4.02 (m,2H), 3.85 (s, 6H). HRMS calcd for C 31 H 28 NO5 + 494.1967[M+1] + ; found, 494.1975.

[0075] Synthesis of compound 7: The same method as that used for the synthesis of compound 5 in Example 1 was employed. After deprotection with hydrochloric acid, the compound was separated by column chromatography (petroleum ether / ethyl acetate = 1 / 1, v / v) to obtain a pale yellow solid 7. 1 H NMR (300 MHz, DMSO-d6) δ 10.05 (s,1H), 9.24 (s, 1H), 8.42 (d, J = 8.6 Hz, 1H), 8.13 – 7.83(m, 11H), 7.30 (s,2H), 6.81 (s, 1H), 3.85 (s, 6H). HRMS calcd for C 29 H 24 NO4 + 450.1705[M+1] + ;found, 450.1716.

[0076] Synthesis of compound BMO-Py-OX: Under nitrogen protection, compound 7 (0.32 g, 0.71 mmol) was dissolved in ethanol (10 mL), and sodium carbonate aqueous solution (1.5 mol / L, 4 mL) was added. With thorough stirring, excess hydroxylamine hydrochloride (0.73 g, 10.65 mmol) was added, and the mixture was heated to 60°C. o C reaction. After 11 h, the starting material was consumed. After removing the ethanol by rotary evaporation, an appropriate amount of dichloromethane (12 mL) was added, and the mixture was washed three times with water (10 mL each time). The organic phases were combined and dried. After removing the solvent by rotary evaporation, the mixture was separated by column chromatography (dichloromethane / methanol = 8 / 1, v / v) to give a nearly white solid BMO-Py-OX (0.24 g, yield: 70.6%). 1H NMR (400 MHz, DMSO-d6) δ11.75 (s, 1H), 8.99 (s, 1H), 8.15 (s, 1H), 8.04 (d, J = 8.4 Hz, 2H), 7.92 (d,J = 3.0 Hz, 1H),7.91 – 7.88 (m, 5H), 7.83 (s, 2H), 7.49 (s, 1H), 7.30 (d, J =2.3 Hz, 2H), 6.72 (d, J = 2.3 Hz, 1H), 3.85 (s, 6H). 13 C NMR (101 MHz, DMSO-d6)δ 167.67, 161.13, 160.69, 149.15, 147.80, 144.20, 135.13, 131.95, 130.28,129.21,127.81, 127.39, 120.33, 111.91, 106.79, 105.57, 104.48, 69.54, 61.02,56.06, 55.73, 45.80. HRMS calcd for C29H25N2O4 + , 465.1814[M+1] + ; found, 465.1821.

[0077] The 1H NMR spectrum of compound BMO-Py-OX is as follows: Figure 4 As shown, the carbon NMR spectrum is as follows: Figure 5 As shown.

[0078] Synthesis of compound BMO-Py-M-OX: Under nitrogen protection, compound BMO-Py-OX (0.16 g, 0.34 mmol) was dissolved in acetonitrile (10 mL) for chromatography, and iodomethane (0.07 g, 0.51 mmol) was added. The mixture was refluxed. After 9 h, the starting material was completely consumed. After removing the acetonitrile by rotary evaporation, an appropriate amount of dichloromethane (10 mL) was added, and the mixture was washed three times with 10 mL of water each time. The organic phases were combined and dried. After removing the dichloromethane by rotary evaporation, column chromatography (dichloromethane / methanol / ammonia = 90 / 9 / 1, v / v) was performed to give a pale yellow solid BMO-Py-M-OX (0.12 g, yield: 73.8%). 1H NMR (300 MHz, DMSO-d6) δ 13.17 (s, 1H), 9.51 (s,1H), 8.96 – 8.89 (m, 1H), 8.74 (s, 1H), 8.43 (d, J = 8.6 Hz, 1H), 8.10 – 7.97(m, 8H), 7.91 (d, J = 8.4 Hz, 2H), 7.83 – 7.75 (m, 1H), 7.29 (d, J = 2.2 Hz, 1H), 7.11 – 7.07 (m, 1H), 4.47 (s, 3H), 3.85 (s, 6H). 13 C NMR (75 MHz, DMSO-d6)δ 161.21, 144.95, 144.06, 142.02, 141.30,138.17, 130.30, 128.28, 128.03,127.69, 125.31, 106.83, 105.53, 56.08, 46.92. HRMS calcd for C 30 H 27 N2O4 + 479.1965 [M] + ; found, 479.1969.

[0079] Example 3

[0080] Fenitrothion (122-14-5) was selected as a model substrate for the catalytic degradation of organophosphorus pesticides. The model reaction was performed as follows: following the literature method ( J Mol Liq (2017, 243, 178-186), Tetrabutylammonium chloride vesicle media were prepared under ultrasonic conditions at 60℃ (the stock solution concentration was 1.5 M, and it was diluted to the test concentration of 0.05 M with sodium borate buffer solution (0.5 M, pH=9.0) before use. This concentration is 1.2 times the critical micelle concentration of TBACI vesicles to ensure stable micelle dispersion).

[0081] The KCl concentration was tested at 0.1 M. BTFM-Py-OX (15 mg, 0.028 mmol) was weighed and dissolved in sodium borate buffer (3 mL, 0.5 M, pH=9.0). After thorough sonication, the pale yellow solution was added to the aforementioned vesicle medium, followed by the addition of the substrate fenitrothion (3.9 mg, 0.014 mmol). The reaction was rapidly stirred at 25 °C. Substrate consumption and the formation of degradation product OX-P-664 were monitored by LC-MS.

[0082]

[0083] Example 4

[0084] Similar to Example 3, BTFM-Py-M-OX (15 mg, 0.027 mmol) was weighed and dissolved in sodium borate buffer solution (3 mL, 0.5 M, pH=9.0). After ultrasonic mixing, the quaternary ammonium salt solution was added to the surfactant vesicle medium, followed by the addition of fenitrothion (3.7 mg, 0.0135 mmol), and the mixture was rapidly stirred at 25°C. Substrate consumption and the formation of degradation product OX-P-679 were monitored by LC-MS.

[0085]

[0086] Example 5

[0087] As in Example 3, BMO-Py-OX (15 mg, 0.032 mmol) was weighed and dissolved in sodium borate buffer solution (0.5 M, pH=9.0). After ultrasonic mixing, the quaternary ammonium salt solution was added to the surfactant vesicle medium, and fenitrothion (4.4 mg, 0.016 mmol) was added. The mixture was stirred rapidly at 25°C, and substrate consumption and the formation of degradation product OX-P-588 were monitored by LC-MS.

[0088]

[0089] Example 6

[0090] As in Example 3, BMO-Py-M-OX (15 mg, 0.031 mmol) was weighed and dissolved in sodium borate buffer solution (0.5 M, pH=9.0). After ultrasonic mixing, the quaternary ammonium salt solution was added to the surfactant vesicle medium, and fenitrothion (4.3 mg, 0.0155 mmol) was added. The mixture was stirred rapidly at 25°C, and substrate consumption and the formation of degradation product OX-P-603 were monitored by LC-MS.

[0091]

[0092] Following the aforementioned procedures, under the micelle concentration conditions described above, the degradation reaction under micelle catalysis was continuously monitored by liquid chromatography-mass spectrometry (LC-MS) at pH = 9.0. Preliminary results (Table 1) show that, compared to the traditional degrader 2-pyridinecarboxaldehyde oxime iodomethane (2-PAM), the bis(trifluoromethyl) derivative BTFM-Py-M-OX responded faster, the product was quickly detected, and the degradation rate was faster. In contrast, the bis(methoxy) derivatives BMO-Py-OX and BMO-Py-M-OX showed worse overall responses and degradation rates than the bis(trifluoromethyl) derivatives, with BMO-Py-OX exhibiting the worst response and a poorer mass spectrometric response in its degradation product. This indicates that strong electron-withdrawing groups significantly promote the generation of oxime anions, while electron-donating groups inhibit their formation. Therefore, derivatives containing strong electron-withdrawing groups exhibit higher degradation activity in the nucleophilic attack reaction of phosphate ester bonds. Meanwhile, quaternization has little effect on the response of compounds containing strong electron-withdrawing groups, but it can significantly improve the response of compounds containing electron-donating groups. The overall degradation response of quaternary ammonium salts is better than that of non-quaternary ammonium salt pyridinaldehyde oxime derivatives.

[0093] Table 1. Comparison of oxime derivative degradation data under pH = 9.0 condition

[0094]

[0095] Among them, the mass spectrometry of BTFM-Py-OX degradation of fenitrothion products (instrument not calibrated) is as follows: Figure 6 As shown, the mass spectrum (overall) of the BTFM-Py-OX degradation product of fenitrothion is as follows: Figure 7 As shown, the mass spectrum (partial) of the BTFM-Py-OX degradation product of fenitrothion is as follows: Figure 8 As shown.

[0096] Example 7

[0097] Based on the screening results of the aforementioned model reactions, the bis(trifluoromethyl)-substituted compound BTFM-Py-M-OX, which exhibited superior degradation activity, was selected for in-situ reaction with organophosphorus pesticides. Simultaneously, real-time dynamic comparative monitoring of UV-fluorescence spectra was conducted (temperature: 25℃; [fenitrothion] = 100-300 μM, [OX...). − [KCl] = 0.5 mM, [KCl] = 0.1 M, pH 9.0.), to evaluate its feasibility of application in degrading organophosphorus pesticides in real environmental samples.

[0098] Ultraviolet spectroscopy shows, for example Figure 9 As shown, by Figure 9It is known that the p-nitrophenolic compounds produced during the degradation of fenitrothion exhibit a characteristic absorption peak at 406 nm. UV titration experiments showed that the intensity of this absorption peak significantly increased with increasing initial pesticide concentration, confirming the real-time occurrence of the hydrolysis reaction. However, the response of the main degradation product, the oxime-phospholipid structure, in the UV spectrum may be masked by p-nitrophenol, or its response may be weak, making it difficult to effectively track its concentration changes. Therefore, limited by the lower sensitivity limit of UV spectroscopy, it is difficult to meet the needs of monitoring trace pesticide degradation in environmental samples.

[0099] Fluorescent titration experiment (temperature: 25°C; [fenitrothion] = 1-50 μM, [OX) − [KCl] = 50 μM, [KCl] = 0.1 M, excitation wavelength 325 nm; slit width 10, 10; pH 9.0.) Results are as follows: Figure 10 As shown, by Figure 10 It is known that fenitrothion exhibits specific interactions with the target compound within a concentration range of 1-50 μM. Among these, Figure 11 and Figure 12 Elemental composition analysis of the directly extracted fluorescent in-situ titration solution. Figure 11 Elemental composition analysis of BTFM-Py-OX fluorescent in situ titration solution. Figure 12 Elemental composition analysis of the fluorescent in-situ titration solution of BTFM-Py-M-OX was performed, confirming the formation of the main degradation substrate. With increasing pesticide concentration gradient, the fluorescence emission peak of BTFM-Py-M-OX exhibited a significant redshift: the maximum emission wavelength systematically redshifted from 439 nm in the initial blank state to 492 nm, a shift of 53 nm. This significant fluorescence spectral change originates from the nucleophilic addition reaction between the fenitrothion-phosphite group and the oxime fragment of BTFM-Py-M-OX, a reaction process that effectively disrupts the intramolecular charge transfer (ICT) effect of the target molecule. Furthermore, as the conjugated aromatic ring structure of BTFM-Py-M-OX is further increased, the redshift is further enhanced, and the extension of the conjugated system further amplifies the perturbation of the ICT effect. This provides a highly sensitive analytical window for the trace detection of fenitrothion and provides theoretical support for the naked-eye degradation identification of organophosphorus pesticides in the visible light region.

[0100] This invention develops novel derivatives by introducing long-conjugated aryl hydrophobic groups into the molecular structure of oxime derivatives. Under micellar catalysis, the new derivatives, with improved lipophilicity, significantly enhance binding efficiency and degradation performance with pesticides. Simultaneously, by precisely controlling the intramolecular push-pull electron effect of the target derivative, the aryl conjugated π system is significantly extended, promoting a redshift in the fluorescence emission wavelength of the target analyte, establishing a highly sensitive fluorescence detection method to compensate for the shortcomings of traditional UV analysis. Furthermore, through electronic effect optimization, the solubility, stability, and other physicochemical parameters of the compound are significantly improved. This structure-performance synergistic optimization strategy significantly enhances the targeted degradation ability and in vivo bioactivity of oxime derivatives, providing a reliable solution for the effective degradation of opioids in real samples.

[0101] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. It can be applied to various fields suitable for the present invention. Other modifications can be readily made by those skilled in the art. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and examples shown and described herein.

Claims

1. An oxime compound for use in degradation of organophosphorus pesticides, characterized by, It is , , or .

2. Use of the oxime compound for degradation of organophosphorus pesticides according to claim 1 in the detection and degradation of organophosphorus pesticides.

3. Use of the oxime compound for degradation of organophosphorus pesticides according to claim 1 in the preparation of a visualization kit, test paper, colorimetric card or test card for the detection of organophosphorus pesticides, a portable detection device, a synergist for use with the compound, a remediation agent for environmental media contaminated with organophosphorus pesticides.

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