Preparation method and application of dehydrorotaxene derivative

Abstract

The invention discloses a preparation method and application of a dehydrorotaxene derivative. According to the method, acetylenic bonds are introduced into a double-bond conjugated system through olefin hydrocarbon activation alkynylation reaction, then ring closing reaction is completed under the Glaser-Hay coupling condition, so that synthesis of dehydrorotaxene is achieved, and the problems that dehydrorotaxene synthesis steps are tedious, and atom economy is poor are solved. The method for synthesizing dehydrorotaxene is high in atom utilization rate and good in functional group compatibility. The compound prepared by the invention has certain adsorption capacity on iodine simple substances, is physical adsorption, and has application potential of adsorbing radioactive iodine in nuclear waste.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a dehydroannulene derivative and application thereof. BACKGROUND

[0002] Dehydroannulene is a core material for organic electronics due to its highly conjugated macrocyclic skeleton and tunable electronic structure, which can be used to prepare high-mobility OFET (organic field-effect transistor), high-efficiency OLED (organic light-emitting diode) and organic solar cell acceptor layer. Meanwhile, it can be used as a supramolecular host-guest recognition host, metal catalytic ligand, and after functional modification, it can also be used as a targeted drug carrier and a photodynamic therapy reagent for biological medicine, and it can also be used as a comonomer to prepare high-performance conjugated polymers. The traditional synthesis of dehydroannulene is difficult due to the large ring strain of the macrocyclic skeleton, the high unsaturation and poor stability of the product, and the easy oxidation, rearrangement or polymerization. The traditional dehydrogenation and halogen elimination method has poor regioselectivity and positional selectivity, and is easy to generate isomer mixtures. The preparation of the precursor is complicated, the reaction conditions are harsh, the functional group compatibility is poor, the total yield is low, and it is difficult to scale up (M. M. Haley. Chem. Rev. 2006, 106, 5344.).

[0003] Carbon-hydrogen bond activation functionalization reaction has the advantages of good atom economy, strong substrate universality, good selectivity and precise synthesis compared with traditional organic synthesis. Our group has made a series of progress in the research of olefin carbon-hydrogen activation alkylation, sulfonylation, arylation, and alkyne functionalization (Xu, Y.-H.; Loh, T. P. J. Am. Chem. Soc. 2015, 137, 3169.; Xu, Y.-H.; Loh, T. P. Angew. Chem. Int. Ed. 2017, 56, 5091.; Xu, Y.-H.; Loh, T. P. Angew. Chem. Int. Ed. 2018, 57, 555.; Xu, Y.-H.; Loh, T. Org. Lett. 2022, 24, 1979.; Xu, Y.-H. JACS. Au. 2025, 5, 6370.). Due to the advantages of carbon-hydrogen activation alkyne functionalization reaction, C-H alkyne functionalization can be achieved in one step without pre-activation of the substrate, which is highly atom-economic and greatly simplifies the synthesis steps; the regioselectivity and positional selectivity can be precisely controlled to reduce the generation of isomers; the reaction conditions are mild, the functional group compatibility is good, the total yield is significantly improved, and it is easy to scale up; and the dehydroannulene structure diversity can be expanded by multi-substitution and heteroatom doping. We designed a new synthesis method for synthesizing dehydroannulene derivatives based on the olefin carbon-hydrogen activation alkyne functionalization reaction.

[0004] Dehydroannulenes, as a class of molecules with unique structures and interesting electronic properties, have seen significant progress in recent years in terms of synthetic strategies, new structure creation, and property studies. In the creation of novel macrocycles, Xia Haiping's research group used a cycloaddition reaction to introduce a metal (Os) into the annulene ring for the first time

[15] , and this planar metal

[15] annulene exhibited aggregation-induced emission (Xia, H.-P. Nature. 2025, 641, 106.). Researchers have precisely modified the annulene skeleton through mature organic reactions (such as Suzuki coupling), which lays a solid foundation for regulating its physicochemical properties and realizing functional applications (such as serving as the core skeleton of drug active molecules or a building block of functional materials). Current research on dehydroannulenes mainly focuses on the development of efficient synthetic methods, the purposeful design of annulene molecules, and the precise control of their optical and magnetic properties, enabling them to move from theoretical research to practical applications. At the same time, these unique molecules can be used as core units to construct novel organic functional materials, such as supramolecular assemblies and organic semiconductors (OA Stasyuk. Carbon. 2023, 215, 118460.).

[0005] Therefore, it is essential to develop a simple and efficient method for synthesizing dehydroannulene. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing dehydroannulene derivatives and their applications. This invention introduces an alkyne bond into a double-bonded conjugated system through an olefin hydrocarbon-activated alkynylation reaction, followed by a cyclization reaction under Glaser-Hay coupling conditions to achieve the synthesis of dehydroannulenes. This overcomes the problems of cumbersome synthesis steps and poor atom economy in traditional dehydroannulene methods. This method achieves high atom utilization and good functional group compatibility in the synthesis of dehydroannulenes.

[0007] The method for preparing the dehydroannulene derivative of the present invention includes the following steps:

[0008] Step 1: Under nitrogen protection, compound 2 was synthesized by HWE reaction using ethyl (E)-4-(diethoxyphosphoryl)but-2-enoate and compound 1 as raw materials, sodium hydride as base, and tetrahydrofuran as solvent.

[0009] Step 2: Under nitrogen protection, using compound 2 as raw material, DIBAL-H as reducing agent, and tetrahydrofuran as solvent, and controlling the temperature at -78℃, compound 3 was obtained through reduction reaction.

[0010] Step 3: Under nitrogen protection, compound 3 and (bromoethynyl)triisopropylsilane were used as raw materials, tetrabutylammonium acetate and potassium carbonate were used as additives, and isopropanol was used as solvent. The reaction was carried out at 60°C for 72 h in the presence of a palladium catalyst to obtain compound 4.

[0011] Step 4: Under nitrogen protection, compound 4 and acetic anhydride were used as raw materials, triethylamine as base, DMAP as additive, and dichloromethane as solvent to react and obtain compound 5.

[0012] Step 5: Using compound 5 as a raw material and tetrahydrofuran as a solvent, TBAF is added to treat it for desilication to obtain compound 6.

[0013] Step 6: Using compound 6 as a raw material, TMEDA as a ligand and base, and acetone as a solvent, compounds 7 and 8 were obtained through a coupling reaction.

[0014] The reaction route is shown below:

[0015]

[0016] Where Ar represents or .

[0017] In step 3, the palladium catalyst is palladium(II) acetate.

[0018] In step 3, the molar ratio of compound 3 to (bromoethynyl)triisopropylsilane is controlled at 1:6; the molar ratio of compound 3 to palladium(II) acetate is controlled at 1.0:0.1; the molar ratio of compound 3 to potassium carbonate is controlled at 1:2; and the molar ratio of compound 3 to tetrabutylammonium acetate is controlled at 1:1.

[0019] In step 3, the concentration of compound 3 in isopropanol is controlled at 0.2 M.

[0020] In step 6, the reaction is carried out in the presence of a copper catalyst, namely cuprous iodide (I).

[0021] In step 6, the molar ratio of compound 6 to cuprous iodide (I) is controlled at 1:2; the molar ratio of compound 6 to TMEDA is controlled at 1:5.

[0022] In step 6, the concentration of compound 6 in acetone is controlled at 0.05 M.

[0023] Depending on the structure of compound 1, the structural formulas of the dehydroannulene derivatives prepared by the method of the present invention include the following:

[0024]

[0025] This invention employs a multi-step synthetic method, achieving the synthesis of a dehydroarnoin derivative under conditions of olefin hydrocarbon activation alkynylation and Glaser-Hay coupling. It boasts broad substrate applicability, requires no pre-functionalization, and exhibits high atom economy, outperforming traditional synthetic methods in many aspects. This invention provides a novel synthetic approach for dehydroarnoins, possessing both atom economy and promising industrial application prospects.

[0026] The compound prepared by this invention has a certain adsorption capacity for elemental iodine and the adsorption is physical, which has the potential to adsorb radioactive iodine in nuclear waste. Attached Figure Description

[0027] Figure 1 It represents the amount of iodine adsorbed by compound 7-1 over time.

[0028] Figure 2 The image shows a comparison of the infrared spectra of compound 7-1 and compound 7-1 after iodine adsorption.

[0029] Figure 3 This is a thermogravimetric analysis comparison between compound 7-1 and compound 7-1 after iodine adsorption.

[0030] Figure 4 The results show the PXRD analysis of compound 7-1 before and after iodine adsorption. Detailed Implementation

[0031] The technical solution of the present invention will be further analyzed and explained through specific embodiments below.

[0032] Example 1: Synthetic routes of dehydroannulene derivatives 7-1 and 8-1

[0033]

[0034] Step 1: Prepare a 250 mL round-bottom flask and add a suitable magnetic stir bar. First, add NaH (2.4 equiv), purge the flask three times with nitrogen in a double-row tube, and then add THF (0.2 M). Next, place the flask in an ice-water bath at 0°C and slowly add ethyl (E)-4-(diethoxyphosphoryl)but-2-enoate (2.5 equiv) dropwise. The resulting suspension continues to react at this temperature for 30 min. Then, place the above solution at -30°C and slowly add terephthalaldehyde (1) (20 mmol dissolved in 50 mL tetrahydrofuran 0.4 M). After the addition is complete, place the reaction at room temperature for 4 h. Detect the reaction by TLC until it is complete. After the reaction is complete, quench the reaction with saturated sodium bicarbonate, and obtain compound 2 in 52% yield by extraction, drying, concentration, and column chromatography. 1 1H NMR and carbon NMR (13 Chemical shift and coupling constant of C NMR: 1 H NMR (600 MHz, CDCl3) δ 7.44-7.40 (m, 6H), 6.90-6.79 (m,4H), 6.00-5.97 (d, J = 15.3 Hz, 2H), 4.22 (q, J = 7.1 Hz, 4H), 1.31 (t, J =7.1 Hz, 6H). 13 C NMR (151 MHz, CDCl3) δ 166.85, 144.24, 139.43, 136.64, 127.59, 126.84, 121.77, 60.33, 14.32. Identified as compound 2.

[0035]

[0036] Step 2: Under nitrogen protection, a suitable magnetic stir bar was added to a 250 mL round-bottom flask, followed by the sequential addition of compound 2 (9.7 mmol) and THF (0.2 M). The reaction apparatus was placed at -78°C. After 10 min, DIBAL-H (4.5 equiv) was slowly added dropwise. After the addition was complete, the mixture was stirred at -78°C for 0.5 h. The reaction was then carried out at room temperature for 4 h. Subsequently, the reaction was quenched by adding 60 mL (1 M) of sodium hydroxide solution to the mixture at -78°C. After 0.5 h, the reaction was carried out at room temperature, and a saturated potassium sodium tartrate solution and ethyl acetate were added. The mixture was stirred until the suspension was completely dissolved, and then extracted with ethyl acetate. The resulting organic phase was dried and the solvent was removed using a rotary evaporator to obtain compound 3, which required no further separation or purification.

[0037]

[0038] Step 3: Add a suitable magnetic ball to a 100 mL round-bottom flask. Then add the unpurified compound 3 from the previous step, palladium acetate (0.1 equiv), potassium carbonate (2.0 equiv), and tetrabutylammonium acetate (1.0 equiv) sequentially. Evacuate the double-row tubes three times with nitrogen. Add (bromoethynyl)triisopropylsilane (6.0 equiv) and isopropanol (0.2 M). Incubate the reaction at 60 °C for 72 h, monitoring the reaction by TLC. After the reaction, filter the reaction solution through silica gel and diatomaceous earth. Remove the solvent from the resulting organic phase using a rotary evaporator, and then separate by column chromatography to obtain the target compound 4 in 62% yield. The 1H NMR spectrum (1H NMR) was then analyzed. 1 H NMR) and carbon nuclear magnetic resonance (NMR)13 Chemical shifts and coupling constants of C NMR: 1 H NMR (400 MHz, CDCl3) δ 7.47 – 7.36 (m, 6H), 6.70 – 6.65 (m, 4H), 4.25 (s, 4H), 1.16 (s, 42H). 13 C10 NMR (101 MHz, CDCl3) δ 136.92, 135.92, 134.36, 127.03, 126.81, 124.46, 103.51, 99.97, 65.52, 18.74, 11.32. Identified as compound 4.

[0039]

[0040] Step 4: Add a suitable magnetic stir bar to a 100 mL flask, then add compound 4 (2.3 mmol), DMAP (0.2 equiv), and after purging with nitrogen three times using a double-row tube, add triethylamine (4.0 equiv), acetic anhydride (3.0 equiv), and dichloromethane (0.038 M) sequentially. React at room temperature for 2 h, quench the reaction with saturated ammonium chloride, extract the organic phase with dichloromethane, remove the solvent using a rotary evaporator, and separate by column chromatography to obtain target compound 5 by near-equivalent reaction. The result was obtained by proton nuclear magnetic resonance spectroscopy (1H NMR). 1 1H NMR and carbon NMR ( 13 Chemical shift and coupling constant of C NMR: 1 H NMR (400 MHz, CDCl3) δ 7.44-7.36 (m, 6H), 6.73-6.62 (m, 4H), 4.69 (s, 4H), 2.11 (s, 6H), 1.15 (s, 42H). 13 C10 NMR (101 MHz, CDCl3) δ 170.55, 138.36, 136.92, 135.17, 127.14, 126.63, 119.42, 103.26, 99.70, 66.33, 20.89, 11.31. Identified as compound 5.

[0041]

[0042] Step 5: Add a suitable magnetic stir bar to a 100 mL flask, add compound 5 (2 mmol), tetrahydrofuran (0.1 M), and TBAF (3.0 equiv). Initiate the reaction at room temperature for 0.5 h. Then, remove the tetrahydrofuran using a rotary evaporator. Add ethyl acetate to the reaction mixture, wash three times with water to remove TBAF, dry the organic phase, and remove the organic solvent using a rotary evaporator. Separate compound 6 by column chromatography in 95% yield. The result was obtained by proton NMR spectroscopy (1H NMR spectroscopy). 1 HNMR and carbon NMR (H2Nm) 13 Chemical shifts and coupling constants of C NMR: 1 H NMR (400 MHz, CDCl3) δ7.43 (s, 4H), 7.31-7.27 (dd, J = 15.5, J = 11.1 Hz, 2H), 6.78-6.68 (m, 4H), 4.68 (s, 4H), 3.42 (s, 2H), 2.13 (s, 6H). 13 C10 NMR (101 MHz, CDCl3) δ 170.60, 140.06, 136.80, 136.36, 127.36, 125.86, 117.56, 84.97, 80.30, 66.45, 20.95. Identified as compound 6.

[0043]

[0044] Step 6: Add a suitable magnetic stir bar to a 25 mL flask, add compound 6 (0.3 mmol), acetone (0.05 M), cuprous iodide (2.0 equiv), and TMEDA (5.0 equiv), and react for 12 h under atmospheric conditions. After the reaction, filter through diatomaceous earth and silica gel to obtain the organic phase. Remove the organic phase using a rotary evaporator, and then separate compound 7-1 and compound 8-1 by column chromatography in 25% yield and 5% yield, respectively. The results were analyzed by 1H NMR spectroscopy (1H NMR spectroscopy). 1 1H NMR and carbon NMR ( 13 The chemical shifts and coupling constants of compound 7 were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS): 1 H NMR (600 MHz, CDCl3) δ 7.69 (dd, J = 15.4, 11.2 Hz, 4H), 7.65(s, 8H), 6.65-6.59 (m, 8H), 4.66 (s, 8H), 2.13 (s, 12H).13 C NMR (151 MHz, CDCl3) δ 170.54, 141.71, 138.19, 136.95, 127.96, 125.96, 117.07, 81.81,66.56, 20.96. HRMS (ESI) (m / z) : Calcd for C 48 H 40 O4 [M+Na] + : 767.2615, found: 767.2607. Compound 8: 1 H NMR (600 MHz, CDCl3) δ 7.46 (s, 12H), 7.30 (dd, J = 15.5,11.2 Hz, 6H), 6.82-6.74 (m, 12H), 4.68 (m, 12H), 2.13 (s, 18H). 13 C NMR (151MHz, CDCl3) δ 170.54, 142.15, 136.97, 136.95, 127.57, 126.33, 117.66, 81.59,81.07, 65.91, 20.95. HRMS (ESI) (m / z) : Calcd for C 72 H 60 O 12 [M+Na] + : 1139.3977, found: 1139.3984. Identified as target product compounds 7-1 and 8-1.

[0045] Example 2: Synthetic routes of dehydroannulene derivatives 7-2 and 8-2

[0046]

[0047] Step 1: Prepare a 250 mL round-bottom flask and add a suitable magnetic stir bar. First, add NaH (2.4 equiv), purge the flask three times with nitrogen in a double-row tube, and then add THF (0.2 M). Next, place the flask in an ice-water bath at 0°C and add (E)-4-(diethoxyphosphoryl)but-2-enoate ethyl ester (2.5 equiv) dropwise. The resulting suspension is allowed to react at this temperature for 30 min. Then, compound 9 (7 mmol dissolved in 50 mL tetrahydrofuran, 0.14 M) is added dropwise to the above solution at -30°C. After 30 min, the reaction is allowed to proceed at room temperature for 4 h. The reaction is monitored by TLC until completion. After the reaction is complete, the reaction is quenched with saturated sodium bicarbonate, and compound 10 is obtained in 51% yield by extraction, drying, concentration, and column chromatography. 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shifts were identified by C NMR. 1 H NMR (401 MHz, CDCl3) δ 7.37 (dd, J = 15.3, 11.2, 2H), 7.05 (s, 2H), 6.97 (d, J =15.3, 2H), 6.66 (dd, J = 15.2, 11.2 Hz, 2H), 5.97 (d, J = 15.3, 2H), 4.23 (q,J = 7.1 Hz, 4H), 1.31 (t, J = 7.1 Hz, 9H). 13 C NMR (101 MHz, CDCl3) δ 166.88, 143.60, 142.43, 132.25, 129.48, 126.85, 121.64, 60.39, 29.68. The result was that of target compound 10.

[0048]

[0049] Step 2: Under nitrogen protection, compound 10 (3.6 mmol) and THF (0.2 M) were added sequentially to a 100 mL round-bottom flask with a suitable magnetic stir bar. The reaction apparatus was placed at -78 °C. After 10 min, DIBAL-H (4.5 equiv) was slowly added dropwise. After the addition was complete, the mixture was stirred at -78 °C for 0.5 h. Then, the mixture was placed at room temperature for 4 h. The reaction was then quenched by adding 60 mL (1 M) of sodium hydroxide solution to the mixture at -78 °C. After 0.5 h, the mixture was placed at room temperature, and saturated potassium sodium tartrate solution and ethyl acetate were added. The mixture was stirred until the suspension was completely dissolved, and then extracted with ethyl acetate. The resulting organic phase was dried and the solvent was removed using a rotary evaporator. No further separation or purification was performed.

[0050]

[0051] Step 3: Add a suitable magnetic ball to a 100 mL round-bottom flask. Then add the unpurified compound 11 from the previous step, palladium acetate (0.1 equiv), potassium carbonate (2.0 equiv), and tetrabutylammonium acetate (1.0 equiv) sequentially. Evacuate the double-row tubes three times with nitrogen. Add (bromoethynyl)triisopropylsilane (4.0 equiv) and isopropanol (0.2 M). Incubate the reaction at 60 °C for 72 h, monitoring the reaction by TLC. After the reaction, filter the reaction solution through silica gel and diatomaceous earth. Remove the solvent from the resulting organic phase using a rotary evaporator, and then separate by column chromatography to obtain the target compound 12 in 44% yield. The 1H NMR spectrum was then analyzed. 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shifts were identified by C NMR. 1 H NMR (600 MHz, CDCl3) δ 7.09 (dd, J = 15.4, 11.0 Hz, 2H), 6.95 (s,2H), 6.75 (d, J = 15.5 Hz, 2H), 6.59 (d, J = 11.1 Hz, 2H), 4.23 (s, 4H), 1.14(s, 42H). 13 C10 NMR (151 MHz, CDCl3) δ 142.43, 135.39, 127.81, 127.44, 126.26, 124.00, 103.41, 100.46, 65.73, 18.75, 11.29. The result was identified as target compound 12.

[0052]

[0053] Step 4: Add a suitable magnetic stir bar to a 100 mL flask, then add compound 12 (0.74 mmol), DMAP (0.02 equiv), and nitrogen gas three times using a double-row tube. Then add triethylamine (4.0 equiv), acetic anhydride (3.0 equiv), and dichloromethane (0.038 M) sequentially. React at room temperature for 4 h. Quench the reaction with saturated ammonium chloride. Extract the organic phase with dichloromethane, remove the solvent using a rotary evaporator, and separate by column chromatography to obtain the target compound 13 by near-equivalent reaction. The result was obtained by proton nuclear magnetic resonance spectroscopy (NMR). 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shifts were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (400 MHz, CDCl3) δ 7.08 (dd, J= 15.4, 11.0 Hz, 2H), 6.96 (s, 2H), 6.77 (d, J = 15.4 Hz, 2H), 6.57 (d, J =11.0 Hz, 2H), 4.67 (s, 4H), 2.10 (s, 6H), 1.14 (s, 42H). 13 HRMS (ESI) (m / z) : Calcd for C 40 H 60 O4SSi2[M+H] + : 693.3824, found : 693.3829. The identification result is target compound 13.

[0054]

[0055] Step 5: Add a suitable magnetic stir bar to a 25 mL flask, add compound 13 (0.5 mmol), tetrahydrofuran (0.1 M), and TBAF (3.0 equiv). Initiate the reaction at room temperature for 0.5 h. Then, remove the tetrahydrofuran using a rotary evaporator. Add ethyl acetate to the reaction mixture, wash three times with water, and remove the organic solvent using a rotary evaporator. The product after removing the organic phase is not further processed. Add a suitable magnetic stir bar to a 50 mL flask, add the untreated compound 14, and then add acetone (0.05 M), cuprous iodide (2.0 equiv), and TMEDA (5.0 equiv). Initiate the reaction at atmospheric pressure for 12 h. After the reaction, filter through diatomaceous earth and silica gel to obtain the organic phase. After removing the organic phase using a rotary evaporator, column chromatography yields compound 7-2 in 14% yield and compound 8-2 in 17% yield. The organic phase is then analyzed by 1H NMR spectroscopy. 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The chemical shift and coupling constant of compound 7-2 were analyzed by C NMR, and the molecular weight was determined by high-resolution mass spectrometry (HRMS). 1 H NMR (600 MHz, CDCl3) δ 7.37 (dd, J = 15.3, 11.2 Hz, 4H), 7.33 (s, 4H), 6.73 (d, J = 15.3Hz, 4H), 6.61 (d, J = 11.2 Hz, 4H), 4.63 (s, 8H), 2.11 (s, 12H). 13 C NMR (151MHz, CDCl3) δ 170.52, 142.60, 141.05, 129.95, 127.84, 126.45, 117.45, 82.07,81.56, 66.23, 20.94. HRMS (ESI) (m / z): Calcd for C 44 H 36 O8S2[M+Na] + : 779.1744, found : 779.1750. Compound 8-2: 1 H NMR (600 MHz, CDCl3) δ 6.99 – 6.91 (m, 12H), 6.84 (d, J = 15.3 Hz, 6H), 6.68 (d, J = 11.0 Hz, 6H), 4.63 (s, 12H), 2.14 (s,18H). 13C NMR (151 MHz, CDCl3) δ 170.49, 143.04, 141.17, 130.38, 129.63,125.61, 117.32, 82.23, 81.55, 65.94, 20.98. HRMS (ESI) (m / z) : Calcd forC 66 H 54 O 12 S3[M+H] + : 1135.2850, found : 1135.2809. Identified as compounds 7-2 and 8-2.

[0056] Applied Research: Iodine Adsorption Research

[0057] The radioactive iodine in nuclear waste is mainly iodine-131 and iodine-129, with significant variations in content depending on the type of nuclear waste and storage time. Iodine-131 has a half-life of only 8.02 days, and its concentration is high in the early stages of nuclear waste, leading to rapid decay. Iodine-129 has a half-life exceeding 15.7 million years, with each gram of spent fuel containing only a few nanograms to micrograms of radioactive iodine, exhibiting low concentrations but long-term stability. The core hazard of radioactive iodine is its susceptibility to uptake by the human thyroid gland. Iodine-131 releases β and γ rays in a short period, directly damaging thyroid cells and causing inflammation, nodules, and even cancer. Iodine-129 releases radiation over a long period and can accumulate through the food chain, polluting water, soil, and ecosystems, posing a long-term potential radiation risk to humans and the environment. (PE Ron. Radiat. Res. 2006, 166, 715.; DM Taylor. Radioanal. Chem. 1981, 65, 195.). Therefore, it is necessary to study the adsorption of radioactive iodine. Here, we use the cavity of compound 7-1 to study the adsorption capacity of iodine.

[0058] The experimental steps are as follows: Take four 250 mL Erlenmeyer flasks and add 500 mg of granular iodine to each flask. Take four 5 mL glass bottles and add 10 mg of compound 7-1 to each of the four glass bottles. Do not seal the glass bottles. Then place the four glass bottles into the four Erlenmeyer flasks and seal the Erlenmeyer flasks. Number the four Erlenmeyer flasks as 1, 2, 3, and 4, respectively. After placing them in a 75℃ oven, weigh the contents of the glass bottle in Erlenmeyer flask No. 1 after 1 hour, weigh the contents of the glass bottle in Erlenmeyer flask No. 2 after 2 hours, weigh the contents of the glass bottle in Erlenmeyer flask No. 3 after 3 hours, and weigh the contents of the glass bottle in Erlenmeyer flask No. 4 after 4 hours.

[0059] The results were as follows: after 1 hour, the mass of the substance in the glass bottle of conical flask No. 1 was 13.2 mg; after 2 hours, the mass of the substance in the glass bottle of conical flask No. 2 was 14.7 mg; after 3 hours, the mass of the substance in the glass bottle of conical flask No. 3 was 16.4 mg; and after 4 hours, the mass of the substance in the glass bottle of conical flask No. 4 was 16.5 mg. Since the initial amount of compound 7-1 was 10 mg, the difference shows that the amount of iodine adsorbed by compound 7-1 was 3.2 mg after 1 hour, 4.7 mg after 2 hours, 6.4 mg after 3 hours, and 6.5 mg after 4 hours. Adsorption capacity is defined as the ratio of the adsorbed mass of iodine to the mass of compound 7-1. Therefore, the adsorption capacity of compound 7-1 after 1 hour is 0.32 (g / g), after 2 hours it is 0.47 (g / g), after 3 hours it is 0.64 (g / g), and after 4 hours it is 0.65 (g / g). By plotting the adsorption capacity over time, the following values ​​are obtained: Figure 1 .

[0060] Infrared spectroscopy analysis was performed on compound 7-1 and the adsorbed iodine compound 7-1 to obtain... Figure 2 Analysis of infrared spectral results: The red curve is the infrared spectrum of compound 7-1, and the black curve is the infrared spectrum of the complex of iodine and compound 7-1. It can be seen that there is no obvious change in the curve before and after adsorption. There is no CI bond signal at wavenumbers of 500-600, and the ester group signal does not change before and after. It can be determined that the adsorption of iodine by compound 7-1 is physical adsorption.

[0061] Thermogravimetric analysis was performed on compound 7-1 after adsorption for 4 h. The temperature was increased at 10 °C / min under a nitrogen atmosphere and stopped at 900 °C. The results are shown in [Figure number missing]. Figure 3 Comparison of thermogravimetric analysis results: In the thermogravimetric analysis curves, the red curve represents compound 7-1 as a control, and the black curve represents compound 7-1 adsorbing iodine. When the mass loss of compound 7-1 is 5%, the weight loss of the adsorption complex of iodine and compound 7-1 is about 55%.

[0062] Powder X-ray diffraction comparison was performed on compound 7-1 and compound 7-1 with adsorbed iodine. The results are shown in the figure. Figure 4 Powder X-ray diffraction analysis: The red curve represents compound 7-1, and the black curve represents the complex of compound 7-1 and iodine. The disappearance of the diffraction signal indicates that iodine is randomly distributed in the cavity of compound 7-1.

[0063] Based on the above results, it can be seen that the compound prepared by the present invention has a certain adsorption capacity for elemental iodine and the adsorption is physical, thus having the potential to adsorb radioactive iodine from nuclear waste.

Claims

1. A process for the preparation of a dehydrocyclopentaen derivative, characterized in that Comprising the following steps: Step 1: under the protection of nitrogen, (E)-ethyl 4-(diethoxyphosphoryl)but-2-enoate and compound 1 are used as raw materials, sodium hydride is used as base, tetrahydrofuran is used as solvent, and compound 2 is synthesized through HWE reaction; Step 2: under the protection of nitrogen, compound 2 is used as raw material, DIBAL-H is used as reducing agent, tetrahydrofuran is used as solvent, the temperature is controlled at-78℃, and compound 3 is obtained through reduction reaction; Step 3: under the protection of nitrogen, compound 3 and (bromoethynyl) triisopropylsilane are used as raw materials, tetrabutylammonium acetate and potassium carbonate are used as additives, isopropyl alcohol is used as solvent, and compound 4 is obtained in the presence of palladium catalyst at 60℃; Step 4: under the protection of nitrogen, compound 4 and acetic anhydride are used as raw materials, triethylamine is used as base, DMAP is used as additive, and dichloromethane is used as solvent, and compound 5 is obtained through reaction; Step 5: compound 5 is used as raw material, tetrahydrofuran is used as solvent, TBAF is added for desiliconization treatment, and compound 6 is obtained; Step 6: compound 6 is used as raw material, TMEDA is used as ligand and base, and compound 7 and compound 8 are obtained through coupling reaction in acetone; The reaction route is as follows: ； wherein Ar represents or .

2. The preparation method according to claim 1, characterized in that: In step 3, the palladium catalyst is palladium (II) acetate.

3. The preparation method according to claim 1, characterized in that: In step 3, the molar ratio of compound 3 to (bromoethynyl) triisopropylsilane is controlled to be 1:6; the molar ratio of compound 3 to palladium (II) acetate is controlled to be 1.0:0.1; the molar ratio of compound 3 to potassium carbonate is controlled to be 1:2; and the molar ratio of compound 3 to tetrabutylammonium acetate is controlled to be 1:

1.

4. The preparation method according to claim 3, characterized in that: In step 3, the concentration of compound 3 in isopropyl alcohol is controlled to be 0.2 M.

5. The preparation method according to claim 1, characterized in that: In step 6, the reaction is carried out in the presence of copper catalyst, and the copper catalyst is cuprous iodide (I).

6. The preparation method according to claim 5, characterized in that: In step 6, the molar ratio of compound 6 to cuprous iodide (I) is controlled to be 1:2; and the molar ratio of compound 6 to TMEDA is controlled to be 1:

5.

7. The preparation method according to claim 6, characterized in that: In step 6, the concentration of compound 6 in acetone is controlled to be 0.05 M.

8. A dehydrocyclopenta e derivative, obtainable by a process according to any one of claims 1 to 7, characterized in that selected from the following compounds: 。 9. The application of the dehydrogenated wheel alkene derivative in iodine elemental adsorption according to claim 8.

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