A bis-1,2,3-triazole-bisalkyl alcohol derivative, its preparation method and application in nuclide extraction

Abstract

The application discloses a kind of double-1,2,3-triazole-bisalkyl alcohol derivatives and preparation method and application in nuclide extraction, belong to the field of chemical synthesis and applied chemistry field, the present application with double end chain alkynol-containing nitrogen hetero six-membered ring and azido group-containing alcohol as raw material, with active copper as catalyst, azide-alkyne ring addition reaction is carried out in solvent, and double-1,2,3-triazole-bisalkyl alcohol derivatives are creatively generated, and it is found through experiment that the above-mentioned double-1,2,3-triazole-bisalkyl alcohol derivatives have good effect in nuclide extraction, and can effectively separate radioactive element uranium in seawater.

Description

Technical fields:

[0001] This invention belongs to the fields of chemical synthesis and applied chemistry, specifically relating to a bis-1,2,3-triazole-dialkyl alcohol derivative, its preparation method, and its application in radionuclide extraction. Background technology:

[0002] There are two main approaches to developing nuclear energy: fission of heavy elements, such as uranium, and fusion of light elements, such as deuterium, tritium, and lithium. Uranium is currently the most important nuclear fuel; however, uranium reserves on land are not abundant and are extremely unevenly distributed. In contrast, the vast ocean contains abundant uranium resources. It is estimated that the amount of uranium dissolved in seawater could reach 4.5 billion tons, equivalent to several thousand times the total land reserves. If all the uranium in seawater could be extracted, the fission energy it contains could guarantee humanity's energy needs for tens of thousands of years. However, the concentration of uranium in seawater is very low; 1000 tons of seawater contain only 3 grams of uranium. Uranium must first be extracted from seawater before it can be used. Extracting uranium from seawater is technically very difficult, requiring the processing of large quantities of seawater and involving highly complex processes. However, many methods for extracting uranium from seawater have been tested, such as adsorption, co-precipitation, bubble separation, and algal bioconcentration. The treatment of radioactive wastewater generated during nuclear energy development is also receiving increasing attention. Among various purification methods, extraction is one of the most efficient and simple methods used in organic chemistry laboratories to purify and refine compounds. Since extraction utilizes the difference in solubility or partition coefficient of a substance in two immiscible or slightly soluble solvents to transfer the solute from one solvent to another, it does not cause any change in the chemical composition of the extracted substance during the operation, thus completely preserving the chemical properties of the desired substance.

[0003] Based on this, the purpose of this invention is to develop a bis-1,2,3-triazole-dialkyl alcohol derivative by studying the radioactive element uranium used in nuclear reactions. This derivative can be used as an effective solvent for radionuclide extraction, and a simple and efficient preparation method is provided. Summary of the Invention:

[0004] In view of the shortcomings of existing compounds, a first aspect of the present invention is to provide a bis-1,2,3-triazole-dialkyl alcohol derivative.

[0005] A bis-1,2,3-triazole-dialkyl alcohol derivative has the following structural formula:

[0006]

[0007] In the formula: R is selected from pyridine or phenanthroline; R' is selected from ethyl, propyl, hydroxypropyl, 3-(2-oxo-2-((1,2,3-trihydroxypropyl-2-yl)amino)ethyl).

[0008] Furthermore, the present invention also provides the following specific compounds:

[0009]

[0010]

[0011] A second aspect of the present invention is to provide a method for preparing the above-mentioned compound, characterized by comprising the following steps: using a six-membered aza-containing ring containing a di-terminal alkyne and an alcohol containing an azide group as raw materials, and using active copper as a catalyst, performing an azide-alkyne cycloaddition reaction in a solvent to prepare a bis-1,2,3-triazole-dialkyl alcohol derivative.

[0012] The reaction equations involved are as follows:

[0013]

[0014] In the formula: R is selected from pyridine or phenanthroline; R' is selected from ethyl, propyl, hydroxypropyl, 3-(2-oxo-2-((1,2,3-trihydroxypropyl-2-yl)amino)ethyl).

[0015] Furthermore, in the preparation method:

[0016] The nitrogen-containing six-membered ring containing a double-ended alkyne is selected from 2,6-dieethynylpyridine or 2,9-dieethynyl-1,10-phenanthroline.

[0017] The alcohol containing the azido group is selected from 2-azidoethanol, 3-azidopropanol, 3-azido-1,2-propanediol or 2-azido-N-(1,3-dihydroxy-2-(hydroxymethyl)propane-2-yl)acetamide.

[0018] The active copper is selected from monovalent copper salts, preferably cuprous iodide.

[0019] The solvent is selected from N,N-dimethylformamide, preferably a mixture of N,N-dimethylformamide and triethylamine.

[0020] The molar ratio of the nitrogen-containing six-membered ring with double-ended alkynes, the alcohol containing azide groups, and the catalyst is 1:1 to 3:0.08 to 0.09.

[0021] The reaction temperature is 50–80°C, and the reaction time is 12–48 hours. Preferably, the reaction is carried out at 60°C for 20 hours.

[0022] After the reaction is completed, the product is post-processed, including extraction and washing.

[0023] Furthermore:

[0024] This invention provides a method for preparing bis-1,2,3-triazole-dialkyl alcohol derivatives, characterized by comprising the following steps:

[0025] (1) In a 50 ml reaction flask, sodium azide is dissolved in N,N-dimethylformamide. Stirring is started, and 2-bromoethanol is slowly added to the reaction flask under argon atmosphere. After reacting at 60 °C for 48 hours, the mixture is cooled to room temperature to obtain 2-azidoethanol. The molar ratio of sodium azide to 2-bromoethanol is 1.5:1. N,N-dimethylformamide is used as the reaction solvent, and the amount added is 5-10 eq, which is enough to completely dissolve the reactants.

[0026] (2) The 2-azidoethanol obtained in step (1) can be directly used in the reaction in step (2) without post-treatment. 2,6-Diethynylpyridine is added to 2-azidoethanol, followed by triethylamine and cuprous iodide as catalysts. Stirring is started, and the reaction is carried out at 60°C for 20 hours under argon conditions. The molar ratio of 2-azidoethanol to 2,6-diethynylpyridine is 2:1, and N,N-dimethylformamide is still used as the reaction solvent.

[0027] (3) Add concentrated hydrochloric acid to the solution after the reaction in step (2), mix thoroughly, and then ionize the product. Then extract with saturated brine and ethyl acetate, and retain the aqueous phase. Add sodium hydroxide to the aqueous phase, dissolve it thoroughly, and then extract with ethyl acetate, retain the organic phase, dry with anhydrous sodium sulfate, and remove the organic solvent under reduced pressure to obtain 2,2'-(pyridine-2,6-dimethylbis(1H-1,2,3-triazol-4,1-dimethyl))bis(ethane-1-ol).

[0028] A third aspect of this invention aims to provide an application of bis-1,2,3-triazole-dialkyl alcohol derivatives in radionuclide extraction, specifically including the following steps:

[0029] (1) Carboxylated graphene oxide was prepared by reacting succinic acid peroxide with graphene oxide.

[0030] (2) Bis-1,2,3-triazole-dialkyl alcohol derivatives are immobilized on the carboxylated graphene oxide prepared above by esterification reaction. The excellent stability of graphene can preserve the compound for a long time. In addition, due to the excellent adsorption and desorption properties and surface extensibility of graphene, the contact area and extraction efficiency can be effectively increased during the extraction process.

[0031] (3) The carboxylated graphene oxide immobilized with bis-1,2,3-triazole-dialkyl alcohol derivatives was dissolved in ethyl acetate, a small amount of sodium hydroxide was added, and then extracted with seawater with a slightly higher uranium content to separate the organic phase and the aqueous phase; the addition of sodium hydroxide can reverse the esterification reaction, and the bis-1,2,3-triazole-dialkyl alcohol derivatives immobilized on the graphene oxide were separated and dissolved in the organic solution;

[0032] (4) The aqueous phase and organic phase separated after extraction were filtered through a membrane filter with a pore size of 22 μm to further filter out the graphene solid and the separation liquid was retained. The absorbance of the separation liquid was measured by a spectrophotometer. The test results showed that the uranium content in the separation liquid had been significantly reduced.

[0033] The beneficial effects of this invention are as follows:

[0034] (1) The present invention creatively generates a bis-1,2,3-triazole-dialkyl alcohol derivative.

[0035] (2) The present invention provides a simple, efficient and low-cost method for synthesizing the above-mentioned compounds.

[0036] (3) This invention provides an application of bis-1,2,3-triazole-dialkyl alcohol derivatives in radionuclide extraction. Experiments have shown that the above compounds have a good effect in radionuclide extraction and can effectively separate the radioactive element uranium from seawater. Attached image description:

[0037] Figure 1 The 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol) prepared in Example 1 1 H-NMR spectrum.

[0038] Figure 2 The 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol) prepared in Example 1 13 C-NMR spectrum.

[0039] Figure 3a These are the ultraviolet spectra of simulated seawater before extraction with uranium contents of 0, 5 ppm, 10 ppm, and 50 ppm, respectively.

[0040] Figure 3b These are the ultraviolet spectra of the separated liquids after extraction from simulated seawater with uranium contents of 5 ppm, 10 ppm, and 50 ppm. Detailed implementation method:

[0041] The present invention will be further described below with reference to specific embodiments and accompanying drawings:

[0042] Example 1: Preparation of 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol)

[0043] (1) Synthesis of 2-azidoethanol

[0044] In a 50 ml reaction flask, 2.35 g (36 mmol) of sodium azide was dissolved in 20 ml of N,N-dimethylformamide. Stirring was started, and under argon atmosphere, 1.7 ml (24 mmol, ρ = 1.763 g / ml) of 2-bromoethanol was slowly added to the reaction flask. After reacting at 60 °C for 48 hours, the mixture was cooled to room temperature to obtain 2-azidoethanol. No further processing of the product was required.

[0045]

[0046] (2) Synthesis of 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol)

[0047] Add 1.5 g (11.8 mmol) of 2,6-diethynylpyridine to the reaction flask containing the 2-azidoethanol obtained in (1), then add 1 ml of triethylamine and 200 mg of cuprous iodide, start stirring, and stir the reaction at 60 °C for 20 hours under argon atmosphere, then cool to room temperature. 2 ml of concentrated hydrochloric acid (12 mol / L) was added to the reaction solution, and the first step of extraction was performed with saturated brine and ethyl acetate. The aqueous phase was collected, and 2 g of sodium hydroxide was added to the aqueous phase. After complete dissolution, the second step of extraction was performed with ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain 3.42 g of crude 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol). The crude product was washed with 10 ml of solution (n-pentane:dichloromethane = 1:1), and the organic solvent was removed under reduced pressure to obtain 3.39 g of pure 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol), with a yield of 95.5%. 1 H-NMR (400MHz, D2O) δ8.47 (s, 2H), 7.93 (q, J=7.80Hz, 1H), 7.77 (d, J=7.86Hz, 2H), 4.62 (q, J=5.03Hz, 4H), 4.08 (q, J=5.18Hz, 4H). 13 C-NMR (101MHz, D2O) δ148.4, 146.7, 138.8, 124.3, 119.8, 60.1, 52.7.

[0048]

[0049] Example 2: Preparation of 4,4'-(2,6-pyridinidyl)bis[1H-1,2,3-triazol-1-propanol]

[0050] In a 100 ml reaction flask, 1.5 g (11.8 mmol) of 2,6-diethynylpyridine was dissolved in 40 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. Stirring was started, and 2.4 g (23.6 mmol) of 3-azidopropanol was slowly added under argon atmosphere. The reaction was carried out at 60 °C for 20 hours, and then cooled to room temperature. 2 ml of concentrated hydrochloric acid (12 mol / L) was added to the reaction solution, and the first step of extraction was performed with saturated brine and ethyl acetate. The aqueous phase was collected, and 2 g of sodium hydroxide was added to the aqueous phase. After complete dissolution, the second step of extraction was performed with ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain 3.69 g of crude product 2:4,4'-(2,6-pyridinidyl)bis[1H-1,2,3-triazol-1-propanol]. The crude product was washed with 16 ml of solution (n-pentane:dichloromethane = 1:1), and the organic solvent was removed under reduced pressure to obtain 3.65 g of pure product, with a yield of 93.8%. 1 H NMR (D2O, 400MHz), δ = 8.47 (s, 2H), 8.01 (d, 2H, J = 7.5Hz), 7.95 (t, 1H, J = 7.5Hz), 4.58 (t, 4H, J = 6.6Hz), 3.60 (s, 4H), 2.12 ~ 2.19 (m, 4H).

[0051]

[0052] Example 3: Preparation of 3,3-[2,6-pyridinidylbis(1H-1,2,3-triazol-4,1-diyl)]bis[1,2-propanediol]

[0053] In a 50 ml reaction flask, 1.5 g (11.8 mmol) of 2,6-diethynylpyridine was dissolved in 25 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. Stirring was started, and under argon atmosphere, 2.76 g (23.6 mmol) of 3-azido-1,2-propanediol was slowly added. The reaction was carried out at 60 °C for 20 hours, and then cooled to room temperature. Add 2 ml of concentrated hydrochloric acid (12 mol / L) to the reaction solution, and perform a first-step extraction with saturated brine and ethyl acetate. Collect the aqueous phase, then add 2 g of sodium hydroxide to the aqueous phase. After complete dissolution, perform a second-step extraction with ethyl acetate. Dry the resulting organic phase with anhydrous sodium sulfate and remove the organic solvent under reduced pressure to obtain 4.19 g of crude compound 3: 3,3-[2,6-pyridinidylbis(1H-1,2,3-triazol-4,1-diyl)]bis[1,2-propanediol]. Wash the crude product with 16 ml of solution (n-pentane:dichloromethane = 1:1) and remove the organic solvent under reduced pressure to obtain 4.13 g of pure compound 3, with a yield of 97.0%. 1 H NMR (D2O, 400MHz) δ = 8.26 (s, 2H), 7.71 (t, J = 7.6Hz, 1H), 7.54 (d, J = 7.6Hz, 2H) ,4.46-4.51(m,2H),4.35-4.37(m,2H),4.08-4.12(m,2H),3.50-3.57(m,4H).

[0054]

[0055] Example 4: Preparation of 4,4'-(2,6-pyridinidyl)bis[N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]-1H-1,2,3-triazole-1-acetamide]

[0056] In a 100 ml reaction flask, 1.5 g (11.8 mmol) of 2,6-diethynylpyridine was dissolved in 40 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. Stirring was started, and under argon atmosphere, 4.8 g (23.6 mmol) of 2-azido-N-(1,3-dihydroxy-2-(hydroxymethyl)propane-2-yl)acetamide was slowly added. The reaction was carried out at 60 °C for 20 hours, and then cooled to room temperature. 2 ml of concentrated hydrochloric acid (12 mol / L) was added to the reaction solution, and the first step of extraction was performed with saturated brine and ethyl acetate. The aqueous phase was collected, and 2 g of sodium hydroxide was added to the aqueous phase. After complete dissolution, the second step of extraction was performed with ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain 6.27 g of crude compound 4: 4,4'-(2,6-pyridinidyl)bis[N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]-1H-1,2,3-triazol-1-acetamide]. The crude product was washed with 20 ml of solution (n-pentane:dichloromethane = 1:1), and the organic solvent was removed under reduced pressure to obtain 6.20 g of pure compound 4, with a yield of 98.3%. 1 H NMR (D2O, 400MHz) δ = 8.36 (s, 2H), 8.01 (d, J = 7.6Hz, 2H), 7.83 (t, J = 7.6Hz, 1H), 6.73 (s, 1H), 5.14 (s, 4H), 2.11 (s, 18H).

[0057]

[0058] Example 5: Preparation of 2,2'-((1,10-phenanthroline-2,9-diyl)bis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol)

[0059] In a 50 ml reaction flask, 2.7 g (11.8 mmol) of 2,9-diethynyl-1,10-phenanthroline was dissolved in 20 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. Stirring was started, and 2.1 g (23.6 mmol) of 2-azidoethanol was slowly added under argon atmosphere. The reaction was carried out at 60 °C for 20 hours, and then cooled to room temperature. 2 ml of concentrated hydrochloric acid (12 mol / L) was added to the reaction solution, and the first step of extraction was performed with saturated brine and ethyl acetate. The aqueous phase was collected, and 2 g of sodium hydroxide was added to the aqueous phase. After complete dissolution, the second step of extraction was performed with ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain 4.57 g of crude compound 5: 2,2'-((1,10-phenanthroline-2,9-diyl)bis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol). The crude product was washed with 12 ml of solution (n-pentane:dichloromethane = 1:1), and the organic solvent was removed under reduced pressure to obtain 4.49 g of pure compound 5, with a yield of 94.3%. δH(400MHz; DMSO-d6)9.02(s,2H),8.59(d,J=8.2Hz,2H),8.43(d,J=8.2Hz,2H),8.00(s,2H),5.05(s,2H),4.31-4.35(m,4H),3.32-3.36(m,4H).

[0060]

[0061] Example 6: Preparation of 3,3'-((1,10-o-phenanthroline-2,9-diyl)bis(1H-1,2,3-triazol-4,1-diyl))bis(propane-1,2-diol)

[0062] In a 100 ml reaction flask, 2.7 g (11.8 mmol) of 2,9-diethynyl-1,10-phenanthroline was dissolved in 40 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. The mixture was stirred and 2.76 g (23.6 mmol) of 3-azido-1,2-propanediol was slowly added under argon atmosphere. The mixture was reacted at 60 °C for 20 hours and then cooled to room temperature. Add 2 ml of concentrated hydrochloric acid (12 mol / L) to the reaction solution, perform a first-step extraction with saturated brine and ethyl acetate, retain the aqueous phase, add 2 g of sodium hydroxide to the aqueous phase, dissolve completely, and perform a second-step extraction with ethyl acetate. Dry the resulting organic phase with anhydrous sodium sulfate, remove the organic solvent under reduced pressure, and obtain 5.23 g of crude compound 6: 3,3'-((1,10-o-phenanthroline-2,9-diyl)bis(1H-1,2,3-triazol-4,1-diyl))bis(propane-1,2-diol). Wash the crude product with 16 ml of solution (n-pentane:dichloromethane = 1:1), remove the organic solvent under reduced pressure, and obtain 5.17 g of pure compound 6, with a yield of 94.5%. δH(400MHz; DMSO-d6)8.90(s,2H),8.57(d,J=8.2Hz,2H),8.43(d,J=8.0Hz,2H),7.99(s,2H),5.26(s,2 H),4.93(s,2H),4.56(d,J=11.2Hz,2H),4.36(d,J=11.2Hz,2H),3.89-3.93(m,2H),3.38-3.42(m,4H).

[0063]

[0064] Application Example 1:

[0065] The application of 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol) prepared in Example 1 in radionuclide extraction and purification includes the following steps:

[0066] (1) Take appropriate amounts of hydrogen peroxide, succinic anhydride, and deionized water, and add them to a 50 mL three-necked flask in the ratio of m(H2O2):m(SA):m(H2O) = 1.0:1.3:1.9. Stir in an ice bath (around 8°C) for 3 hours until a white gel appears. After standing for 3 hours, filter under reduced pressure to obtain a solid product. Dry under vacuum at 50°C for 24 hours to obtain succinic anhydride peroxide.

[0067] (2) 0.1 g of graphene oxide (GO) and 20 ml of DMF were added to a 50 ml three-necked flask and ultrasonically dispersed at room temperature for 2 hours to obtain a GO suspension. The temperature was raised to 85 °C and the reaction was carried out for 72 hours. During this process, 0.1 g of succinic acid peroxide was added every 24 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered under reduced pressure to obtain a solid product. The product was repeatedly washed with DMF on a vacuum filtration flask lined with a microporous membrane to remove impurities. The product was then vacuum dried at 80 °C for 12 hours to obtain carboxylated graphene oxide, denoted as GO-COOH. Carboxyl groups are widely distributed on the surface of the graphene molecules in this carboxylated graphene oxide, and all of them are active carboxyl groups.

[0068] (3) Weigh 0.1g of compound 1 prepared in Example 1: 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol) and carry out an esterification reaction under dilute hydrochloric acid conditions. 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol) is covalently immobilized on the graphene molecule. Due to the extensive distribution of carboxyl groups in carboxylated graphene oxide, the esterification reaction can basically completely immobilize 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol) on the surface of graphene oxide without causing the equilibrium to shift to the left and decomposition.

[0069] (4) Dissolve 0.1g of graphene oxide immobilized with 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol) in 200ml of ethyl acetate, add 0.2g of sodium hydroxide, dissolve with ultrasonic assistance, and pour into a 1L separatory funnel;

[0070] (5) Take 200 ml of simulated seawater with a slightly higher uranium content (uranium content: 30 ppm), pour it into a separatory funnel, shake it thoroughly for extraction, let it stand and separate the aqueous phase and organic phase, and separate the aqueous phase and organic phase by high-speed centrifugation to separate the undissolved graphene oxide powder solid. Then, pass the separated liquid through a membrane filter with a pore size of 22 μm to further filter out the unsettled graphene solid. Each separated liquid is used for the detection of uranium content in the liquid.

[0071] (6) Dissolve 0.07 g of azoarsine-III powder in 100 mL of 3 mol / L perchloric acid solution, and dissolve with ultrasonic assistance. After standing for one week, a colorimetric reagent solution is obtained. Mix the aqueous phase separation solution and the colorimetric reagent at a volume ratio of 1:3. Measure the absorbance of the separation solution using a spectrophotometer. The results show that uranyl ions in the aqueous phase separation solution no longer have an absorption peak at the characteristic absorption wavelength of 651 nm, proving that the residual uranyl ions in the solution are below the detection limit of the spectrophotometer, indicating that the uranyl ion content has been significantly reduced.

[0072] (7) According to the formula for calculating the rate of change of uranyl ion concentration:

[0073]

[0074] C0: Initial concentration (ppm), C p Equilibrium concentration (ppm).

[0075] Calculations showed that the adsorption and extraction efficiency of uranyl ions by 2,2'-(pyridine-2,6-dimethylbis(1H-1,2,3-triazol-4,1-dimethyl))bis(ethane-1-ol) reached 96.7%.

[0076] Application Example 2:

[0077] The method is the same as in Application Example 1, except that the type of compound weighed in step (3) is different. Compounds 2-6 prepared in Examples 2-6 are used respectively, and their extraction efficiency for uranyl ions is tested by comparing them with the graphene oxide support, as shown in Table 1:

[0078] Table 1

[0079] Compound type Extraction efficiency / % Graphene oxide carrier 1.2 Compound 2 88.6 Compound 3 97.2 Compound 4 93.6 Compound 5 87.8 Compound 6 92.2 .

[0080] As can be seen from the data in Table 1, the position of the substituents and the number of hydroxyl groups have a significant impact on the extraction efficiency. Compound 3 prepared in Example 3, 3,3-[2,6-pyridinidylbis(1H-1,2,3-triazol-4,1-diyl)]bis[1,2-propanediol], has the best extraction efficiency, reaching 97.2%. Further improvements can be made based on this structure.

[0081] analyze:

[0082] This invention provides a bis-1,2,3-triazole-dialkyl alcohol derivative that can be used as an effective solvent for radionuclide extraction. As can be seen from the above examples, using the compound of this invention for radionuclide extraction has the advantages of simple synthesis method, readily available raw materials, safe and feasible reaction, and extremely high extraction and adsorption rate for uranyl ions.

Claims

1. A method for preparing a bis-1,2,3-triazole-dialkyl alcohol derivative, characterized in that, Includes the following steps: (1) Synthesis of 2-azidoethanol In a 50 ml reaction flask, 2.35 g of sodium azide was dissolved in 20 ml of N,N-dimethylformamide. Stirring was started, and 1.7 ml of 2-bromoethanol was slowly added to the reaction flask under argon atmosphere. After reacting at 60 °C for 48 hours, the mixture was cooled to room temperature to obtain 2-azidoethanol. No post-treatment of the product was required. (2) Synthesis of 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol) Add 1.5 g of 2,6-diethynylpyridine to the reaction flask containing the 2-azidoethanol obtained in step (1), then add 1 ml of triethylamine and 200 mg of cuprous iodide. Start stirring and stir the reaction at 60 °C for 20 hours under argon atmosphere, then cool to room temperature. Add 2 ml of concentrated hydrochloric acid to the solution after the reaction, and perform the first extraction with saturated brine and ethyl acetate, retaining the aqueous phase. Add 2 g of sodium hydroxide to the obtained aqueous phase, dissolve it completely, and then perform the second extraction with ethyl acetate. The obtained organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to give 3.42 g of crude 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol). The crude product was washed with 10 ml of solution, and the organic solvent was removed under reduced pressure to give 3.39 g of pure 2,2'-(pyridine-2,6-diylbis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol), with a yield of 95.5%.

2. A method for preparing a bis-1,2,3-triazole-dialkyl alcohol derivative, characterized in that, Includes the following steps: In a 100 ml reaction flask, 1.5 g (11.8 mmol) of 2,6-diethynylpyridine was dissolved in 40 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. Stirring was initiated, and 2.4 g of 3-azidopropanol was slowly added under argon atmosphere. The reaction was carried out at 60 °C for 20 hours, then cooled to room temperature. 2 ml of concentrated hydrochloric acid was added to the resulting solution, and a first-step extraction was performed using saturated brine and ethyl acetate. The aqueous phase was collected, and 2 g of sodium hydroxide was added to the aqueous phase. After complete dissolution, a second-step extraction was performed using ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain 3.69 g of crude compound 2: 4,4'-(2,6-pyridinidyl)bis[1H-1,2,3-triazol-1-propanol]. The crude product was washed with 16 ml of solution, and the organic solvent was removed under reduced pressure to obtain 3.65 g of pure product, with a yield of 93.8%.

3. A method for preparing a bis-1,2,3-triazole-dialkyl alcohol derivative, characterized in that, Includes the following steps: In a 50 ml reaction flask, 1.5 g of 2,6-diethynylpyridine was dissolved in 25 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. Stirring was initiated, and under argon atmosphere, 2.76 g of 3-azido-1,2-propanediol was slowly added. The reaction was carried out at 60 °C for 20 hours, then cooled to room temperature. 2 ml of concentrated hydrochloric acid was added to the resulting solution, and a first-step extraction was performed using saturated brine and ethyl acetate. The aqueous phase was collected, and then... 2g of sodium hydroxide was added to the aqueous phase and dissolved completely. A second extraction was performed using ethyl acetate. The resulting organic phase was dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain 4.19g of crude compound 3: 3,3-[2,6-pyridinidylbis(1H-1,2,3-triazol-4,1-diyl)]bis[1,2-propanediol]. The crude product was washed with 16ml of solution, and the organic solvent was removed under reduced pressure to obtain 4.13g of pure compound 3, with a yield of 97.0%.

4. A method for preparing a bis-1,2,3-triazole-dialkyl alcohol derivative, characterized in that, Includes the following steps: In a 100 ml reaction flask, 1.5 g of 2,6-diethynylpyridine was dissolved in 40 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. Stirring was initiated, and under argon atmosphere, 4.8 g (23.6 mmol) of 2-azido-N-(1,3-dihydroxy-2-(hydroxymethyl)propane-2-yl)acetamide was slowly added. The reaction was carried out at 60 °C for 20 hours, followed by cooling to room temperature. 2 ml of concentrated hydrochloric acid was added to the resulting solution, and the first extraction step was performed using saturated brine and ethyl acetate. The aqueous phase was collected, and 2g of sodium hydroxide was added to the aqueous phase. After complete dissolution, the mixture was extracted with ethyl acetate in the second step. The resulting organic phase was dried with anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain 6.27g of crude product of compound 4: 4,4'-(2,6-pyridinidyl)bis[N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]-1H-1,2,3-triazol-1-acetamide]. The crude product was washed with 20ml of solution, and the organic solvent was removed under reduced pressure to obtain 6.20g of pure product of compound 4, with a yield of 98.3%.

5. A method for preparing a bis-1,2,3-triazole-dialkyl alcohol derivative, characterized in that, Includes the following steps: In a 50 ml reaction flask, 2.7 g of 2,9-diethynyl-1,10-phenanthroline was dissolved in 20 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. Stirring was started, and under argon atmosphere, 2.1 g of 2-azidoethanol was slowly added. The reaction was carried out at 60 °C for 20 hours, then cooled to room temperature. 2 ml of concentrated hydrochloric acid was added to the resulting solution, and a first-step extraction was performed using saturated brine and ethyl acetate. The aqueous phase was collected, and then... Add 2g of sodium hydroxide, dissolve completely, and then perform a second extraction with ethyl acetate. Dry the resulting organic phase with anhydrous sodium sulfate and remove the organic solvent under reduced pressure to obtain 4.57g of crude compound 5: 2,2'-((1,10-phenanthroline-2,9-diyl)bis(1H-1,2,3-triazol-4,1-diyl))bis(ethane-1-ol). Wash the crude product with 12ml of solution and remove the organic solvent under reduced pressure to obtain 4.49g of pure compound 5, with a yield of 94.3%.

6. A method for preparing a bis-1,2,3-triazole-dialkyl alcohol derivative, characterized in that, Includes the following steps: In a 100 ml reaction flask, 2.7 g of 2,9-diethynyl-1,10-phenanthroline was dissolved in 40 ml of N,N-dimethylformamide, followed by the addition of 1 ml of triethylamine and 200 mg of cuprous iodide. Stirring was initiated, and under argon atmosphere, 2.76 g of 3-azido-1,2-propanediol was slowly added. The reaction was carried out at 60 °C for 20 hours, then cooled to room temperature. 2 ml of concentrated hydrochloric acid was added to the resulting solution, and a first-step extraction was performed using saturated brine and ethyl acetate. The aqueous phase was collected, and then... 2g of sodium hydroxide was added to the phase and dissolved completely. The phase was then extracted with ethyl acetate in the second step. The resulting organic phase was dried with anhydrous sodium sulfate and the organic solvent was removed under reduced pressure to obtain 5.23g of crude product of compound 6: 3,3'-((1,10-o-phenanthroline-2,9-diyl)bis(1H-1,2,3-triazol-4,1-diyl))bis(propane-1,2-diol). The crude product was washed with 16ml of solution and the organic solvent was removed under reduced pressure to obtain 5.17g of pure product of compound 6, with a yield of 94.5%.

7. An application of a bis-1,2,3-triazole-dialkyl alcohol derivative prepared by the method of claims 1-6 in radionuclide extraction, specifically comprising the following steps: (1) Carboxylated graphene oxide was prepared by reacting succinic acid peroxide with graphene oxide. (2) Bis-1,2,3-triazole-dialkyl alcohol derivatives are immobilized on the carboxylated graphene oxide prepared above by esterification reaction. The excellent stability of graphene can preserve the compound for a long time. In addition, due to the excellent adsorption and desorption properties and surface extensibility of graphene, the contact area and extraction efficiency can be effectively increased during the extraction process. (3) The carboxylated graphene oxide immobilized with bis-1,2,3-triazole-dialkyl alcohol derivatives was dissolved in ethyl acetate, a small amount of sodium hydroxide was added, and then extracted with seawater with a slightly higher uranium content to separate the organic phase and the aqueous phase; the addition of sodium hydroxide can reverse the esterification reaction, and the bis-1,2,3-triazole-dialkyl alcohol derivatives immobilized on the graphene oxide were separated and dissolved in the organic solution; (4) The aqueous phase and organic phase separated after extraction were filtered through a membrane filter with a pore size of 22 μm to further filter out the graphene solid and the separation liquid was retained. The absorbance of the separation liquid was measured by a spectrophotometer. The test results showed that the uranium content in the separation liquid had been significantly reduced.

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