Method for detecting nitro-containing compound by K-region tetra-substituted pyrenyl derivative
By connecting conjugated substituents to the K region to expand the π-conjugation system, the tetrasubstituted pyrene derivatives in the K region were synthesized, and the accuracy and sensitivity of the existing methods for detecting nitro compounds were solved, achieving high efficiency and low The cost detection effect has expanded the types of detection substances, which is suitable for industrial promotion.
Patent Information
- Application Number
- CN202411025304.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-30
- Publication Date
- 2024-12-17
AI Technical Summary
The existing methods for detecting nitro compounds have problems such as insufficient accuracy and sensitivity, long response time and high equipment cost. In particular, polycyclic aromatic hydrocarbon compounds are weakened or quenched when interacting with nitro-containing compounds, making it difficult to effectively detect.
By connecting conjugated substituents to the K region to expand the π-conjugation system, 2,7-di-tert-butyl-4,5,9,10-tetrabromopyrene as raw material was designed and synthesized, and K region was prepared by Sonogashira coupling reaction. Tetrasubstituted pyrene derivatives are used for ultra-trace detection of nitro compounds, expanding the types of traditional detection substances and providing new detection methods.
Achieve efficient and low-cost K-zone four-substituted pyrene derivative synthesis, simplify the synthesis steps, improve detection accuracy and sensitivity, reduce pollution, is suitable for industrial applications, and shows great development in ultra-trace detection potential.
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Figure CN119147509A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of luminescent materials, and specifically relates to the synthesis of a K-block tetrasubstituted pyrene derivative and the application of the same in ultra-trace detection of nitro compounds. Background Art
[0002] Given the wide application of nitroaromatic compounds in many fields such as industry, agriculture, and pharmaceutical science, nitroaromatic compounds have become indispensable chemical materials for human survival and industrial development. However, with the widespread use of nitroaromatic compounds, a series of hazards to human health, environmental pollution, and homeland security have followed. For example, some of these compounds have mutagenic or carcinogenic activity through bioaccumulation and reproduction in the food chain. Even trace amounts of aromatic and nitroaromatic derivatives in the environment can lead to serious public health and environmental problems. Therefore, it is urgent to establish some methods that can effectively detect nitro compounds. At present, several feasible methods such as electrochemistry, spectrophotometry, and analytical techniques such as electrochemistry, gas chromatography (GC), and capillary electrophoresis (CE) are used to detect nitro compounds. However, these methods have some disadvantages that cannot be ignored, such as lack of accuracy and sensitivity, long response time, and high cost of instruments and equipment. Polycyclic aromatic hydrocarbons (PAHs) have extended π-conjugated structures, adjustable energy gaps, and high fluorescence quantum yields. At the same time, these compounds are prone to fluorescence weakening or even quenching when interacting with electron-deficient structures such as nitro compounds. As representatives of polycyclic aromatic hydrocarbons, pyrene and its derivatives are widely used in various applications and detection of nitro explosives due to their strong electron-donating properties and high fluorescence efficiency. Based on this theory, one of the main strategies for designing and synthesizing fluorescence quenching of pyrene derivatives of nitro compounds is to detect them. Summary of the invention
[0003] The purpose of the present invention is to expand the π-conjugated system by inserting a conjugated substituent in the K region. This type of molecule has great development potential in ultra-trace detection of nitro compounds; The invention uses 2,7-di-tert-butyl-4,5,9,10-tetrabromopyrene as a raw material, heats and refluxes in an organic solvent, and prepares a K-region tetrasubstituted pyrene derivative through a Sonogashira coupling reaction, thereby providing a new idea for synthesizing pyrene derivatives for detecting nitro compounds.
[0004] In order to broaden the types of compounds containing nitro compounds that can be detected in the traditional method, the present invention proposes a pyrene derivative with the structure formula of detecting nitro compounds:
[0005] The tetrasubstituted pyrene derivatives in the K region have great development potential in the ultra-trace detection of nitro compounds.
[0006] In order to more efficiently prepare the above-mentioned K-region pyrene derivatives capable of detecting nitro compounds, the technical solution of the present invention proposes a method for synthesizing a K-region tetrasubstituted pyrene derivative, comprising the following steps: Step 1: Synthesis: Using compound 1 and 1-alkynylnaphthalene as raw materials, 2,7-di-tert-butyl-4,5,9,10-tetra(naphthalene-1-ethynyl)pyrene is prepared. The reaction formula is:
[0007] Step 2: Extraction: After the reaction is completed, the cooled reaction product is extracted with a good solvent for 2 to 3 times, and the organic phase solution is collected. The collected organic phase solution is washed with saturated brine for 2 to 3 times, and then dried with anhydrous magnesium sulfate to obtain a mixture of the crude reaction product and the good solvent; Step 3: Purification: distill the mixture of the crude reaction product and the good solvent until a small amount of solvent remains, separate by column chromatography, and then rotary evaporate to obtain the pure target product.
[0008] The various raw materials used in the present invention are all commercial reagents with low prices. The intermediates are relatively simple to prepare and have good thermal stability without requiring special storage conditions. The overall synthetic route is simple, the yield is high, and the pollution is low.
[0009] In order to better prepare the tetrasubstituted pyrene derivatives in the K block, the preferred technical scheme is that in the first step, the molar ratio of compound 1 and 1-alkynylnaphthalene is 1:8, the catalyst dosage is 15%, the solvent is triethylamine and N,N-dimethylformamide, the reaction temperature is 100°C, and the reaction time is 24h.
[0010] In order to improve the extraction efficiency of the reactants, a preferred technical solution is that the good solvent in the second step is dichloromethane.
[0011] In order to improve the purification efficiency, the preferred technical solution is that the solvents used for column chromatography are dichloromethane and petroleum ether, and the ratio of dichloromethane to petroleum ether is 1:3.
[0012] In order to better promote the application of this type of pyrene derivatives with the property of ultra-trace detection of nitro compounds, it is proposed that the K-block tetrasubstituted pyrene derivatives have great development potential in the ultra-trace detection of nitro compounds.
[0013] The advantages and beneficial effects of the present invention are: 1. The present invention proposes a tetrasubstituted pyrene derivative in the K region, which expands the types of substances for traditional detection of nitro compounds; the compound has great development potential in ultra-trace detection of nitro compounds.
[0014] 2. The present invention uses compound 1 and 1-ethynylnaphthalene as raw materials and relatively mild reaction conditions to prepare K-block tetrasubstituted pyrene derivatives through Sonogashira coupling reaction, providing a new method for synthesizing pyrene derivatives for ultra-trace detection of nitro compounds.
[0015] 3. The various raw materials used in the synthesis of the present invention are cheap and easy to obtain, the intermediates are simple to prepare and have stable performance, and do not require special storage conditions; the relevant reagents and solvents are commonly used commercial reagents with low cost; the overall synthesis route is simple, the yield is high, and the pollution is small; the synthesis method includes three steps of synthesis, extraction and purification, which simplifies the synthesis steps compared to other synthesized K-block pyrene derivatives, making the method easier to promote industrial application. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 It is the structure of a synthetic compound; Figure 2 It is a bar graph comparing the fluorescence emission spectra of compound 2 in different concentrations (dichloromethane) of different nitro compounds. DETAILED DESCRIPTION
[0017] The specific embodiments of the present invention are further described below in conjunction with the accompanying drawings and examples. The following examples are only used to more clearly illustrate the technical scheme of the present invention, and cannot be used to limit the scope of protection of the present invention. The process, conditions, reagents, experimental methods, test methods, etc. of implementing the present invention, except for the contents specifically mentioned below, are all common knowledge and common common sense in the art, and the present invention has no special restrictions. The data given in the following examples include specific operations and reaction conditions and products. The product purity is identified by nuclear magnetic resonance and high-resolution mass spectrometry, and the structure is accurately characterized.
[0018] A K-block tetrasubstituted pyrene derivative for trace detection of nitro compounds, the structural formula is shown below:
[0019] The synthesis method of the tetrasubstituted pyrene derivative having K region comprises the following steps: Step 1: Synthesis: Compound 1 and acetylenedaphthyl raw material are used to prepare 2,7-di-tert-butyl-4,5,9,10-tetra(naphthalene-1-ethynyl)pyrene through a Sonogashira coupling reaction. The reaction formula is:
[0020] Step 2: Extraction: After the reaction is completed, the cooled reaction product is extracted with a good solvent for 2 to 3 times, and the organic phase solution is collected. The collected organic phase solution is washed with saturated brine for 2 to 3 times, and then dried with anhydrous magnesium sulfate to obtain a mixture of the crude reaction product and the good solvent; Step 3: Purification: distill the mixture of the crude reaction product and the good solvent until a small amount of solvent remains, separate by column chromatography, and then rotary evaporate to obtain the pure target product.
[0021] In order to better prepare the tetrasubstituted pyrene derivatives in the K block, the preferred technical scheme is that in the first step, the molar ratio of compound 1 and 1-ethynyl naphthalene is 1:8, the catalyst dosage is 20%, the solvent is triethylamine and N,N-dimethylformamide, the reaction temperature is 100°C, and the reaction time is 24h.
[0022] In order to improve the extraction efficiency of the reactants, a preferred technical solution is that the good solvent in the second step is dichloromethane.
[0023] In order to improve the purification efficiency, the preferred technical solution is that the solvents used for column chromatography are dichloromethane and petroleum ether, and the ratio of dichloromethane to petroleum ether is 1:3.
[0024] In order to better promote the application of this type of pyrene derivatives with the property of ultra-trace detection of nitro compounds, it is proposed that the K-block tetrasubstituted pyrene derivatives have great development potential in the ultra-trace detection of nitro compounds.
[0025] Example 1 Taking the synthesis of compound 2 as an example, the chemical reaction formula is as follows:
[0026] Compound 1 (200 mg, 0.32 mmol), Et 3 A mixture of N (10 mL) and DMF (10 mL) (V / V=1:1) was stirred, and 1-ethynylnaphthalene (389 mg, 2.56 mmol), cuprous iodide (18.3 mg, 0.096 mmol), bis(triphenylphosphine)palladium dichloride (44.9 mg, 0.064 mmol), and triphenylphosphine (16.8 mg, 0.064 mmol) were added. The mixture was heated to 100 °C and stirred for 24 hours. After the reaction was completed, it was cooled to room temperature and extracted twice with dichloromethane (2× 30 mL). The organic layer was extracted twice with saturated brine (2 ´ 30 mL), dried with magnesium sulfate, and evaporated. Purification was performed by dichloromethane / petroleum ether (1:3) column chromatography.
[0027] 1 H NMR (400 MHz, CDCl 3 ): (δ= ppm): δ H = 1.77 (s, 18H, t Bu), 7.31–7.35(m, 4H, Ph– H), 7.51–7.59 (m, 8H, Ph– H ), 7.93–7.98 (m, 8H, Ph– H ), 8.05 (d, J =4Hz, 4H, Ph– H ), 8.87 (d, J =8 Hz, 4H, Ph– H ), 9.21 (s, 4H, pyrene– H ).
[0028] Example 2 The difference between Example 2 and Example 1 is that the molar ratio of compound 1 to 1-ethynylnaphthalene is 1:7, while that of Example 1 is 1:8. The yield of the separated target compound 2 is 40.6%, and the test data is the same as that of Example 1.
[0029] Example 3 The difference between Example 3 and Example 1 is that the molar ratio of compound 1 to 1-ethynylnaphthalene is 1:9, while that of Example 1 is 1:8. The yield of the separated target compound 2 is 45.1%, and the test data is the same as that of Example 1.
[0030] Example 4 The difference between Example 4 and Example 1 is that the amount of cuprous iodide catalyst used is 25%, while the amount of catalyst used in Example 1 is 30%, and the yield of the separated target compound 2 is 33.6%. The test data is the same as that of Example 1.
[0031] Example 5 The difference between Example 5 and Example 1 is that the amount of catalyst used is 35%, while the amount of catalyst used in Example 1 is 30%, and the yield of the separated target compound 2 is 45.7%. The test data is the same as that of Example 1.
[0032] Example 6 The difference between Example 6 and Example 1 is that the reaction temperature is 90°C, while the reaction temperature of Example 1 is 100°C. The yield of the separated target compound 2 is 36.2%, and the test data is the same as that of Example 1.
[0033] Example 7 The difference between Example 7 and Example 1 is that the reaction temperature is 110°C, while the reaction temperature of Example 1 is 100°C. The yield of the separated target compound 2 is 44%, and the test data is the same as that of Example 1.
[0034] Example 8 The difference between Example 8 and Example 1 is that the reaction time is 16 hours, while the reaction time of Example 1 is 24 hours. The yield of the separated target compound 2 is 35.2%, and the test data is the same as that of Example 1.
[0035] Example 9 The difference between Example 9 and Example 1 is that the reaction time is 32 hours, while the reaction time of Example 1 is 24 hours. The yield of the separated target compound 2 is 45.9%, and the test data is the same as that of Example 1.
[0036] The drugs used in this embodiment are all commercially available chemical reagents.
[0037] The experimental results show that Example 1 is the best reaction synthesis condition. Although the yields of Example 3, Example 5 and Example 9 are slightly higher than that of Example 1, the raw material input amounts of Example 3 and Example 5 are large, and the reaction time of Example 9 is long. Therefore, it is determined that the reaction conditions of Example 1 are the best, that is, the molar ratio of the main reactants is 1:8, the amount of cuprous iodide catalyst is 30%, the reaction temperature is 100°C, and the reaction time is 24h.
[0038] Example 10 Trace detection performance of nitro compounds of target compound 2 in test example 1: Step 1: Prepare the target compound 2 of Example 1 at a concentration of 1×10 -5 When testing nitro compounds, prepare 30 μL of 1×10 -3 moL / L mother solution, and add dichloromethane reagent, and 3mL of dichloromethane solution of five different nitro compounds with different amounts (from 0→1600μmoL), and then perform fluorescence emission spectrum test with the maximum absorption wavelength of the two organic luminescent bodies as the excitation wavelength. ; Step 2: Use a fluorescence spectrometer to perform fluorescence tests on 50 solutions of different concentrations of five nitro compounds to which target compound 2 is added.
[0039] The experimental results show that TNPy p -NA has the best detection effect, with a quenching rate of 99.99%. The quenching rates of the other four nitro compounds are: o -NA is 28.69%, m -NA is 75.42%, p -NT is 9.7%, p -NCB is 1.4%.
Claims
1. A method for detecting nitro-containing compounds using tetrasubstituted pyrene derivatives in the K region, characterized in that: The structural formula of the tetrasubstituted pyrene derivative in the K region is: 。 2. As claimed in claim 1, a method for synthesizing a tetrasubstituted pyrene derivative in the K region, characterized in that: The steps include: Step 1: Synthesis: Using compound 1 and 1-ethynylnaphthalene as raw materials, 2,7-di-tert-butyl-4,5,9,10-tetra(naphthalene-1-ethynyl)pyrene was prepared by Sonogashira coupling reaction. The reaction formula is:
3. The second step: extraction, after the reaction is completed, the cooled reaction product is extracted with a good solvent for 2 to 3 times, the organic phase solution is collected, and the collected organic phase solution is washed with saturated brine for 2 to 3 times in sequence, and then dried with anhydrous magnesium sulfate to obtain a mixture of the crude reaction product and the good solvent; Step 3: Purification: distill the mixture of the crude reaction product and the good solvent until a small amount of solvent remains, separate by column chromatography, and then rotary evaporate to obtain the pure target product.
4. The method for synthesizing the tetrasubstituted pyrene derivative in the K region according to claim 2, characterized in that: In the first step, the molar ratio of compound 1 to 1-ethynylnaphthalene is 1:7-9, the solvent is triethylamine and N,N-dimethylformamide, the reaction temperature is reflux, and the reaction time is 16-32 hours.
5. The method for synthesizing the tetrasubstituted pyrene derivative in the K region according to claim 2, characterized in that: The reaction efficiency is highest when the molar ratio of compound 1 to 1-acetylenonaphthalene is 1:8, the solvents are triethylamine and N,N-dimethylformamide, the reaction temperature is reflux, and the reaction time is 24 hours.
6. The method for synthesizing a tetrasubstituted pyrene derivative in the K region according to claim 2, characterized in that: The good solvent in the second step is dichloromethane.
7. An application of a tetrasubstituted pyrene derivative in the K region, characterized in that: The tetrasubstituted pyrene derivative in the K region as claimed in claim 1 has great development potential in the ultra-trace detection of nitro compounds.