Chlorine-containing monophosphine compound as well as preparation method and application thereof

Abstract

The invention discloses a chlorine-containing monophosphine compound as well as a preparation method and application thereof, and the chlorine-containing monophosphine compound is (2-formyl phenyl) diphenylphosphine-2, 6-dichloro-1, 4-phenylenediamine; the preparation method comprises the following steps: sequentially adding 2, 6-dichloro-1, 4-phenylenediamine and (2-formylphenyl) diphenylphosphine into an organic solvent I in an inert gas atmosphere, reacting for a certain time at a certain temperature, cooling and filtering to obtain a crude product; and dissolving the obtained crude product in a dichloromethane / normal hexane mixed solution, cooling, volatilizing and crystallizing, filtering and drying to obtain the chlorine-containing monophosphine compound. The chlorine-containing monophosphine compound is applied as a fluorescent probe to detect heavy metal ions, and the heavy metal ions in a solution are detected by utilizing the fluorescence intensity enhancement effect of the chlorine-containing monophosphine compound on the heavy metal ions. The preparation method disclosed by the invention is simple and convenient to operate, relatively mild in reaction condition, relatively low in raw material price and low in process cost, and has an application prospect of industrial production.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, and more specifically, this invention relates to a chlorinated monophosphine compound, its preparation method and application. Background Technology

[0002] Organophosphorus compounds have broad application prospects in industrial production and daily life, attracting significant attention in fields such as medical materials, optoelectronic materials, and flame retardant materials. Furthermore, organochlorine compounds generally exhibit unique physicochemical characteristics, which determine their wide application in materials, medicine, and environmental protection. Therefore, the safety monitoring of chlorinated organophosphorus compounds for environmental protection has received widespread attention and research from scientists. Patent CN120025509A discloses an organophosphonate retarder and its preparation method and application; patent CN120058092A discloses an organophosphorus wastewater treatment method and its application; and patent CN120040637A discloses an organophosphonic acid polymer flame retardant and its preparation method and application. These patents demonstrate the broad scientific research significance and rich socio-economic value of organophosphorus compounds. However, the number of new organophosphorus compounds in the existing technology remains relatively small, necessitating the development of more and new organophosphorus compounds. Summary of the Invention

[0003] One object of the present invention is to solve at least the above-mentioned problems and / or defects, and to provide at least the advantages described below.

[0004] To achieve these and other advantages according to the present invention, the present invention provides a chlorinated monophosphine compound, characterized in that the chlorinated monophosphine compound is (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine, the structural formula of which is as follows: .

[0005] A method for preparing a chlorinated monophosphine compound includes the following steps: Step 1: Under an inert gas atmosphere, 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine are added sequentially to organic solvent I. The mixture is reacted at a certain temperature for a certain time, and then cooled and filtered to obtain the crude product. Step 2: Dissolve the crude product obtained in Step 1 in a mixed solution of dichloromethane / n-hexane, cool and volatilize to crystallize, filter and dry to obtain the chlorinated monophosphine compound.

[0006] Preferably, in step 1, the molar ratio of 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine is 1:(0.98~2). Preferably, in step 1, the reaction temperature is 40℃~70℃ and the reaction time is 5 h~8 h.

[0007] Preferably, in step 1, the organic solvent I is ethanol or methanol; and the ratio of 2,6-dichloro-1,4-phenylenediamine to organic solvent I is 5~6 mmol: 20~60 mL.

[0008] An application of a chlorinated monophosphine compound, wherein the chlorinated monophosphine compound is used as a fluorescent probe for detecting heavy metal ions, specifically utilizing the fluorescence intensity enhancement effect of the chlorinated monophosphine compound on heavy metal ions to detect heavy metal ions in solution, wherein the heavy metal ions include Hg. 2+ Cu 2+ Cr 3+ .

[0009] Preferably, the specific method includes: S1. Dissolve the chlorinated monophosphine compound in organic solvent II to prepare a 5×10⁻⁶ solution. -3 mol / L ~ 5×10 -7 Find the ultraviolet absorption peaks of chlorinated monophosphine compounds by using a series of concentration gradients of mol / L. S2. Add mercuric nitrate monohydrate, copper nitrate trihydrate, or chromium nitrate nonhydrate solution to a solution containing a chlorinated monophosphine compound, and test the fluorescence intensity of the mixed solution.

[0010] Preferably, the organic solvent II is N,N-dimethylformamide.

[0011] Preferably, in step S1, the concentration of the chlorinated monophosphine compound solution is 5 × 10⁻⁶. -7 mol / L ~ 5×10 - 3 mol / L; In step S2, after adding solutions of mercuric nitrate monohydrate, copper nitrate trihydrate, and chromium nitrate nonahydrate to the chlorinated monophosphine compound solution, the concentrations of all three hydrates are 5 × 10⁻⁶. - 7 mol / L ~ 5×10 -3 mol / L.

[0012] The present invention has at least the following beneficial effects: 1. This invention has pioneered a method for preparing (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine, filling the gap in (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine among chlorinated p-phenylenediamine monophosphine derivatives, and effectively promoting the development of chlorinated monophosphine compounds.

[0013] 2. In this invention, the product (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine is used as a fluorescent probe to study the interaction between its compound and Hg. 2+ Cu 2+ Cr 3+ Function, detected Hg 2+ Cu 2+ Cr 3+ The fluorescence intensity of all samples was enhanced; detection revealed that (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine has a single crystal structure, is almost free of impurities, and has a very high purity.

[0014] 3. The preparation method described in this invention is simple to operate, has mild reaction conditions, low raw material prices, and low process costs, and has application prospects for industrial production.

[0015] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the synthetic route for the chlorinated monophosphine compound in Example 1; Figure 2 The ultraviolet spectrum of (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine prepared in Example 1; Figure 3 The fluorescence spectrum of (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine prepared in Example 1; Figure 4 The fluorescence spectra of (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine solution with different concentrations of mercuric nitrate added are shown. Figure 5 The fluorescence spectra of copper nitrate at different concentrations were obtained when (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine solution was added; Figure 6 The fluorescence spectra of chromium nitrate added to (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine solution at different concentrations were obtained. Figure 7 The molecular structure diagram of (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine prepared in Example 1. Detailed Implementation

[0017] The present invention will now be described in further detail with reference to the accompanying drawings, so that those skilled in the art can implement it based on the description.

[0018] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof. Example 1 like Figure 1 As shown, a method for preparing a chlorinated monophosphine compound includes the following steps: Step 1: Under a nitrogen atmosphere, 20 mL of ethanol solvent was added to the reactor, followed by the sequential addition of 2,6-dichloro-1,4-phenylenediamine (5.13 mmol, 0.9088 g) and (2-formylphenyl)diphenylphosphine (5.11 mmol, 1.4844 g). The reactor was placed in a heated stirrer at 70 °C. After the reaction was completed in 8 h, 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine were obtained as crude yellow powder products. Step 2: The crude yellow powder products of 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine were filtered while hot and washed three times with anhydrous ethanol. Finally, the powder products were placed in a dry reactor, and a mixed solvent of dichloromethane / n-hexane (10 mL each) was injected. The mixture was stirred until the products were completely dissolved. The product was then filtered to evaporate, cooled to crystallize, and dried to obtain the single crystal target products of 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine (1.8892 g, yield 78.94%).

[0019] Example 2 The reaction was modified from Example 1, except that the reaction was carried out at 40°C. At 40°C, the reaction process was greatly slowed down, and the reaction eventually ended to obtain the target product (0.3772 g, 15.76%).

[0020] Example 3 The experiment was modified from Example 1, except that the reaction time was 5 hours. The reaction was stopped, and the target products with different yields were obtained after the same post-treatment as in Example 1.

[0021] Example 4 The experiment was modified from Example 1, except that the reaction time was 5.5 h. The reaction was stopped, and the target products in different yields were obtained after the same post-treatment as in Example 1.

[0022] Example 5 The experiment was modified from Example 1, except that the reaction time was 6 hours. The reaction was stopped, and the target products with different yields were obtained after the same post-treatment as in Example 1.

[0023] Example 6 The experiment was modified from Example 1, except that the reaction time was 6.5 h. The reaction was stopped, and the target products in different yields were obtained through the same post-treatment as in Example 1.

[0024] Example 7 The experiment was modified from Example 1, except that the reaction time was 7 hours. The reaction was stopped, and the target products with different yields were obtained after the same post-treatment as in Example 1.

[0025] Example 8 The experiment was modified from Example 1, except that the reaction time was 7.5 h. The reaction was stopped, and the target products in different yields were obtained after the same post-treatment as in Example 1.

[0026] Examples 3-8 illustrate that reaction time has a significant impact on yield. When the reaction time is above 5 hours, the target product begins to form, but the yield is low, only reaching 10%–15% (0.2393 g–0.3590 g). When the reaction time reaches 6 hours, the reaction is not completely completed, and only a portion of the target product (1.8892 g, 78.94%) is obtained. As the reaction time increases, the amount of the target product gradually increases. However, with a further increase in reaction time, reaching 7 hours, although the reaction proceeds very fully, detection revealed that the reactant 2,6-dichloro-1,4-phenylenediamine was no longer detectable in the resulting mixed solution. This indicates that all of the reactant 2,6-dichloro-1,4-phenylenediamine has formed the target product, but a high yield was not achieved because prolonged stirring promoted the dissolution of some products in the solvent, resulting in a small amount of the target product obtained after purification. The final yield of the target product only reached 72.54% (1.7360 g). Therefore, the difficulty of purifying the target product needs to be considered, and the reaction time should be controlled within 8 hours.

[0027] Example 9 The experiment was modified from Example 1, except that the amount of ethanol used was changed from 20 mL to 40 mL. The reaction was stopped, and the target products in different yields were obtained after the same post-treatment as in Example 1.

[0028] Example 10 The experiment was modified from Example 1, except that the amount of ethanol used was changed from 20 mL to 60 mL. The reaction was stopped, and the target products in different yields were obtained after the same post-treatment as in Example 1.

[0029] Examples 9 and 10 illustrate that the amount of ethanol used has a significant impact on the yield. When the amount of ethanol gradually increases from 20 mL to 60 mL, the amount of the target product obtained after purification actually decreases. Specifically, when the amount of ethanol is 40 mL, the amount of the target product obtained after purification is 1.7061 g, with a yield of 71.29%; when the amount of ethanol is 60 mL, the amount of the target product obtained after purification is 1.1535 g, with a yield of 48.2%. Analysis revealed that excessive ethanol does not hinder the formation of the target product; its main impact is seen in the purification stage: too much ethanol enhances the solubility of the product, leading to increased product loss during purification and ultimately a decrease in the amount of purified product.

[0030] Example 11 The experiment was modified from Example 1, except that the molar ratio of 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine was changed to 1:1.2. The reaction was stopped, and the target products in different yields were obtained after the same post-treatment as in Example 1.

[0031] Example 12 The experiment was modified from Example 1, except that the molar ratio of 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine was changed to 1:1.5. The reaction was stopped, and the target products in different yields were obtained after the same post-treatment as in Example 1. Example 13 The experiment was modified from Example 1, except that the molar ratio of 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine was changed to 1:2. The reaction was stopped, and the target products in different yields were obtained after the same post-treatment as in Example 1.

[0032] Examples 1 and 11-13 show that when the molar ratio of 2,6-dichloro-1,4-phenylenediamine to (2-formylphenyl)diphenylphosphine changes from 1:0.98 to 1:2, the yield of the target product gradually increases and then plateaus. Beyond 1:2, the yield increase is minimal. Analysis suggests that as the amount of (2-formylphenyl)diphenylphosphine gradually increases, it becomes excessive in the reaction system. This excess ensures complete conversion of the reactant 2,6-dichloro-1,4-phenylenediamine; however, because the amount of 2,6-dichloro-1,4-phenylenediamine was not adjusted synchronously, the yield did not significantly increase when the molar ratio exceeded 1:2. After the reaction is complete, the excess (2-formylphenyl)diphenylphosphine can be dissolved in ethanol solvent without adversely affecting the separation, purification and purity of the target product. Therefore, the yield of the target product gradually stabilizes as the molar ratio of the two is further changed.

[0033] Comparative Example 1 The reaction was modified from Example 1, except that the reaction was carried out at 80°C. At 80°C, the product organophosphorus deteriorates due to the excessively high temperature, and the reaction eventually ends to obtain an oily, unfamiliar product. Therefore, the reaction temperature needs to be below 80°C.

[0034] Application Example 1 The product prepared in Example 1 was subjected to fluorescence detection studies of heavy metal ions, with Hg being selected. 2+ Cu 2+ Cr 3+ For the target ion analysis: Using N,N-dimethylformamide (DMF) as solvent, a (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine fluorescent probe system was prepared, and the fluorescence response characteristics of this product with the target heavy metal ion were systematically investigated.

[0035] The absorption wavelength of the product in Example 1 was found to be 360 ​​nm from ultraviolet spectroscopy. Figure 2 Therefore, excitation was performed at 360 nm, resulting in a fluorescence emission peak of approximately 468 nm for the product. Figure 3 ), belonging to the ILTC transition.

[0036] In the study of fluorescence response characteristics, the concentration of (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine in the solution was 5 × 10⁻⁶. -4 The concentration of product A is mol / L; at the same time, while keeping the concentration of product solution A unchanged, different concentrations of metal ions are added to form mixed solutions B1-B5, C1-C5, and D1-D5.

[0037] like Figure 4 As shown, add 5×10 -4 mol / L ~ 5×10 -8 The fluorescence emission peak of the mixed solution of mercuric nitrate at a concentration of 5 × 10⁻⁶ mol / L is approximately 488 nm. Compared to product A solution, the fluorescence emission peak of the mixed solution is red-shifted by 20 nm, and this is even more pronounced at a mercuric nitrate concentration of 5 × 10⁻⁶ mol / L. - 4 The intensity increased 28.7 times at a concentration of mol / L. However, the concentration of mercuric nitrate was 5 × 10⁻⁶. -5 mol / L ~ 5×10 -8 At a concentration of mol / L, the fluorescence of the mixed solution was quenched. Experimental results indicate that mercuric nitrate at the same concentration as the product readily causes drastic changes in the fluorescence intensity of the mixed solution, making it a potential candidate for mercury detection, and suitable for subsequent Hg testing. 2+ Ion detection.

[0038] like Figure 5As shown, the concentration range introduced into product A solution is 5 × 10⁻⁶. -8 ~5×10 -4 After adding copper nitrate at a concentration of 5 mol / L, the mixed system exhibited a characteristic fluorescence emission peak at 505 nm. Compared with the fluorescence emission peak of product A solution, the emission peak of the mixed solution showed a significant red shift of 37 nm; when the copper nitrate concentration reached 5 × 10⁻⁻⁻⁻⁶ mol / L, the mixed system showed a significant red shift. 5 mol / L-5×10⁻ 4 At a concentration of mol / L, the fluorescence emission intensity of the mixed solution was 9.7 to 20.7 times higher than that of product A solution. However, the concentration of copper nitrate was 5 × 10⁻⁶. -6 mol / L ~ 5×10 -8 At a concentration of mol / L, the fluorescence of the mixed solution is quenched. The reason for this quenching is Cu. + A complex was formed with product A, and the complex did not produce fluorescence emission, thus exhibiting macroscopic fluorescence quenching. Experimental results show that product A solution can enhance the fluorescence properties of high-concentration copper nitrate, while low-concentration copper nitrate easily leads to product quenching.

[0039] like Figure 6 As shown, product A was found to be similar to 5×10 -8 mol / L ~ 5×10 -4 After treatment with mol / L chromium nitrate, a characteristic fluorescence emission peak appeared at 468 nm, without redshift. Only at 5 × 10⁻⁶ mol / L did the fluorescence peak appear. -4 The fluorescence intensity increased 6.93 times at a concentration of mol / L, verifying that product A has a positive effect on Cr. 2+ Its fluorescence response characteristics.

[0040] Single crystals (undried) of (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine prepared in Example 1 were analyzed by X-ray single-crystal diffraction: Relevant crystal structure parameters of the product {(2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine}: C 25 H 19 Cl2N2P (M=449.31g / mol): monoclinic, spacegroup P21 / n, a=9.9852(2)Å, b=10.9792(2)Å, c=20.2352(4)Å, α=90°, β=100.870(2)°, γ=90°, V=2178.53(7)Å 3 Z=4, μ(MoKα)=3.482 mm -1 ,8.9°≤2Θ≤145.94°; R int =0.0266, R sigma=0.0271; R1=0.0385, wR2=0.0975 (I>2σ(I)); R1=0.0508, wR2=0.1037 (all data). Figure 7 The image shows the molecular structure of (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine as determined by a single-crystal structure diffractometer. This demonstrates that the method described in this invention can successfully prepare the compound (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine having the aforementioned structural formula.

[0041] The description of the processing scale herein is intended to simplify the explanation of the invention. Applications, modifications, and variations of the invention will be readily apparent to those skilled in the art.

[0042] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. 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 illustrations shown and described herein.

Claims

1. A chlorinated monophosphine compound, characterized in that, The chlorinated monophosphine compound is (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine, and the structural formula of (2-formylphenyl)diphenylphosphine-2,6-dichloro-1,4-phenylenediamine is as follows: 。 2. A method for preparing a chlorinated monophosphine compound according to claim 1, characterized in that, Includes the following steps: Step 1: Under an inert gas atmosphere, 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine are added sequentially to organic solvent I. The mixture is reacted at a certain temperature for a certain time, and then cooled and filtered to obtain the crude product. Step 2: Dissolve the crude product obtained in Step 1 in a mixed solution of dichloromethane / n-hexane, cool and volatilize to crystallize, filter and dry to obtain the chlorinated monophosphine compound.

3. The method for preparing the chlorinated monophosphine compound according to claim 2, characterized in that, In step 1, the molar ratio of 2,6-dichloro-1,4-phenylenediamine and (2-formylphenyl)diphenylphosphine is 1:(0.98~2).

4. The method for preparing the chlorinated monophosphine compound according to claim 2, characterized in that, In step 1, the reaction temperature is 40℃~70℃ and the reaction time is 5h~8h.

5. The method for preparing the chlorinated monophosphine compound according to claim 2, characterized in that, In step 1, the organic solvent I is ethanol or methanol; the ratio of 2,6-dichloro-1,4-phenylenediamine to organic solvent I is 5~6 mmol: 20~60 mL.

6. An application of the chlorinated monophosphine compound according to claim 1, characterized in that, The chlorinated monophosphine compound is used as a fluorescent probe for detecting heavy metal ions. Specifically, it utilizes the fluorescence intensity enhancement effect of the chlorinated monophosphine compound on heavy metal ions to detect heavy metal ions in solution, including Hg. 2+ Cu 2+ Cr 3+ .

7. The application of the chlorinated monophosphine compound according to claim 6, characterized in that, Specific methods include: S1. Dissolve the chlorinated monophosphine compound in organic solvent II to prepare 5×10⁻⁶ solutions. -3 mol / L-5×10 -7 Find the ultraviolet absorption peaks of chlorinated monophosphine compounds by using a series of concentration gradients of mol / L. S2. Add mercuric nitrate monohydrate, copper nitrate trihydrate, or chromium nitrate nonhydrate solution to a solution containing a chlorinated monophosphine compound, and test the fluorescence intensity of the mixed solution.

8. The application of the chlorinated monophosphine compound according to claim 7, characterized in that, The organic solvent II is N,N-dimethylformamide.

9. The application of the chlorinated monophosphine compound according to claim 7, characterized in that, In step S1, the concentration of the chlorinated monophosphine compound in the chlorinated monophosphine compound solution is 5 × 10⁻⁶. -7 mol / L ~ 5×10 -3 mol / L; In step S2, after adding solutions of mercuric nitrate monohydrate, copper nitrate trihydrate, and chromium nitrate nonahydrate to the chlorinated monophosphine compound solution, the concentrations of all three solutions are 5 × 10⁻⁶. -7 mol / L ~ 5×10 -3 mol / L.

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