CN112479835B - Pentabiphenyl macrocyclic compound and preparation and application thereof - Google Patents
Pentabiphenyl macrocyclic compound and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a pentabiphenyl macrocyclic compound, a preparation method and an application thereof, wherein the pentabiphenyl macrocyclic compound has a structure shown in a formula (I):
the preparation method specifically comprises the following steps: removing methyl from a pentabiphenyl methoxyl monomer compound to obtain a pentabiphenyl full-hydroxyl monomer compound, modifying the pentabiphenyl full-hydroxyl monomer compound to obtain a pentabiphenyl bromine chain monomer compound, and then placing the pentabiphenyl bromine chain monomer compound in an organic solvent to react with paraformaldehyde under the catalysis of a catalyst to obtain the pentabiphenyl macrocyclic compound. Compared with the prior art, the pentabiphenyl macrocyclic compound of the invention shows high-efficiency adsorption to iodine in water and air, can be used as an excellent material for removing iodine in water, adopts commercially available raw materials, is simple and convenient to synthesize, has high yield, is convenient to modify and can be recycled.
Description
Technical Field
The invention belongs to the field of compound synthesis, and particularly relates to a pentabiphenyl macrocyclic compound, and preparation and application thereof.
Background
In a nuclear reactor power plant which has been widely used at present, nuclear fission in a nuclear reactor is accompanied by the generation of a considerable amount of radioactive byproducts, and radioactive iodine among these radioactive byproducts can be converted into gas at 184 ℃, and rapidly diffuses into air and water in accordance with the combustion of fossil fuel, so that there is a risk that the radioactive iodine is very easily released in the event of an accident such as an accident during fuel inspection or exchange, fuel handling, or a nuclear reactor runaway accident. The radioactive iodine having mainly a long half-life 129 I (half-life: 1.57X 10) 7 Year) and short half-life 131 I (half-life: 8.05 days), 129 i is the most threatening to humans because it is present in the environment for a long time, while 131 Although the half-life is short, it is readily bioabsorbed and accumulated, thereby directly affecting human health. Since ordinary iodine is an essential trace element in the human body and is concentrated in the thyroid gland near the throat to become a component of growth hormone, radioactive iodine taken by a person through breathing, water or food is concentrated in the nail-like form as in ordinary iodineIn the gland, internal radioactive irradiation is increased.
Conventionally, there are a washing treatment method, a physicochemical treatment method using a solid adsorbent using fibrous activated carbon or the like as a packed material, a treatment method using an ion exchanger, and the like, but there are also drawbacks associated therewith. As a method put into practical use as a washing treatment method, there is an alkali washing method, in which treatment is performed by a washing treatment method using a liquid adsorbent, and there are many problems in terms of quantity and safety in order to store the treated product in a liquid state for a long period of time. In the physical chemical treatment method using the solid adsorbent packing, there is a possibility that the captured radioactive iodine is often exchanged with other gases, and in addition, there is a difficulty that the adsorbed substance is easily released when the temperature is increased. In the treatment method using an ion exchanger, the heat-resistant temperature of the ion exchanger is only about 100 ℃, and there is a problem that the ion exchanger cannot exhibit sufficient performance at a higher temperature than that. Therefore, finding an excellent adsorbent to capture and store radioactive iodine has important application value.
Patent CN201910975631.8 discloses macrocyclic and cage-like molecules based on biphenyl arene and derivative compounds thereof, and a synthetic method and application thereof. A series of new large rings are mainly obtained by reacting bis- (2, 4-dialkoxyphenyl) arene (naphthalene, anthracene, pyrene, porphyrin and the like) or tris- (2, 4-dialkoxyphenyl) arene (benzene, s-triphenylacene) and paraformaldehyde under the catalysis of Lewis acid with high yield. In addition, full-hydroxy biphenyl aromatic hydrocarbon (quaterphenyl trimerization, naphthalene dimerization and the like) can be obtained by removing methyl, and various water-soluble derivatives can be obtained by further modification. The solubility of the pentabiphenyl macrocycle mentioned in the patent is poor, if the method commonly used in the patent is used, the difficulty of ring closing can be caused, and the solubility of the obtained pentabiphenyl ring is further reduced after the demethoxylation; if the compound containing 12 bromine chains is continuously reacted with the compound, various complex byproducts are generated, so that the reaction is difficult and the separation is difficult. If 2, 4-di (3-bromo-n-propyl) oxyphenylboronic acid with a bromine chain is used and then reacted with 4, 4-dibromoterphenyl to obtain a pentabiphenyl monomer, the cost is high.
Disclosure of Invention
The pentabiphenyl macrocyclic compound shows efficient adsorption to iodine in water and air, can be recycled, can be used as an excellent material for removing radioactive iodine, can be commercially purchased as a raw material, is simple and convenient to synthesize, high in yield, convenient to modify and recyclable.
The purpose of the invention is realized by the following technical scheme:
a pentabiphenyl macrocyclic compound having the structure shown in formula (I):
a preparation method of the pentabiphenyl macrocyclic compound comprises the following specific steps: removing methyl from a pentabiphenyl methoxyl monomer compound to obtain a pentabiphenyl full-hydroxyl monomer compound, modifying the pentabiphenyl full-hydroxyl monomer compound to obtain a pentabiphenyl bromine chain monomer compound, and then placing the pentabiphenyl bromine chain monomer compound in an organic solvent to react with paraformaldehyde under the catalysis of a catalyst to obtain the pentabiphenyl macrocyclic compound.
The preparation method specifically comprises the following steps:
(a) Dissolving a pentabiphenyl methoxyl monomer compound (also called bis- (2, 4-dimethoxyphenyl) terphenyl) and boron tribromide in an organic solvent, reacting, and carrying out post-treatment to obtain the pentabiphenyl total hydroxyl monomer compound shown in a formula (II),
(b) Dissolving the pentabiphenyl full-hydroxy monomer compound obtained in the step (a), 1, 3-dibromopropane and cesium carbonate in an organic solvent, reacting, and carrying out post-treatment to obtain a pentabiphenyl bromine chain monomer compound shown in a formula (III),
(c) And (c) dissolving the pentabiphenyl bromine chain monomer compound obtained in the step (b) and paraformaldehyde in an organic solvent, adding a catalyst, reacting, and performing post-treatment to obtain the pentabiphenyl macrocyclic compound.
In step (a), the reaction is carried out in N 2 Under protection, the reaction temperature is 20-30 ℃, and the reaction time is 30-48h.
In the step (a), methylene chloride is used as the organic solvent.
In the step (a), the post-treatment process specifically comprises the following steps: quenching the reacted reaction solution by ice water.
In the step (a), the adding amount ratio of the pentabiphenyl methoxyl monomer compound, the boron tribromide and the organic solvent is (0.5-1.5) g, (2.0-3.0) mL, (250-350) mL, and the preferable adding amount ratio is 1g:2.4mL:300mL, the molar ratio of the pentabiphenyl methoxy monomer compound to the boron tribromide is preferably 1.
In step (a), boron tribromide attacks the oxygen in the methoxy group as an acid, so that it can be easily removed.
In step (b), reacting in N 2 The reaction is carried out under protection, the reaction temperature is 80-100 ℃, and the reaction time is 10-14h.
In the step (b), acetonitrile is adopted as the organic solvent.
In the step (b), the post-treatment process specifically comprises the following steps: naturally cooling the reaction solution after reaction to room temperature, then carrying out suction filtration to obtain filtrate, and purifying the filtrate by adopting a silica gel column chromatography. And washing the filter cake obtained by suction filtration for multiple times by using dichloromethane, and combining the obtained washing liquid and the filtrate for purification.
In the step (b), the addition amount ratio of the pentabiphenyl full-hydroxyl monomer compound, the 1, 3-dibromopropane, the cesium carbonate and the organic solvent is (0.5-1.5) g, (8-10) g, (3-4) g, (200-300) mL, and the preferable addition amount ratio is 1g:9g:3.6g:250mL, calculated as molar weight, the preferred molar ratio of the pentabiphenyl total hydroxyl monomer compound, 1, 3-dibromopropane and cesium carbonate is 1.
In step (b), cesium carbonate is used as a base.
In the step (c), the reaction temperature is 20-30 ℃, and the reaction time is 20-40min.
In the step (c), the organic solvent is halogenated hydrocarbon, and the halogenated hydrocarbon is selected from one of dichloromethane, dibromomethane, trichloromethane, tribromomethane, carbon tetrachloride, dichloroethane, dibromoethane, trichloroethane, dibromoethane, tetrachloroethane, tetrabromoethane, monochloropropane, monobromopropane, monochlorobutane, monobromobutane, monochloropentane, monobromopentane, monochlorohexane, monobromohexane, monochloroheptane, monobromoheptane, monobromooctane, monochlorooctane, monochloronane, monobromonane, monochlorodecane or monobromodecane.
In the step (c), the catalyst adopts Lewis acid, and the Lewis acid adopts trifluoromethanesulfonic acid.
In the step (c), the post-treatment process specifically comprises the following steps: quenching the reacted reaction solution by adopting a saturated sodium bicarbonate solution, washing by adopting the saturated sodium bicarbonate solution, and purifying the reaction solution by adopting a silica gel column chromatography.
In the step (c), the addition amount ratio of the pentabiphenyl bromine chain monomer compound, the paraformaldehyde and the organic solvent is (0.5-1.5) g, (0.060-0.070) g, (250-350) mL, and the preferable addition amount ratio is as follows: 1g:0.064g:300mL, calculated as molar amounts, the preferred molar ratio of pentabiphenyl bromochain monomer compound to paraformaldehyde is 1: and 2, the solvent is 300mL/mmol (calculated by the pentabiphenyl bromine chain monomer compound).
The application of the pentabiphenyl macrocyclic compound in radioactive iodine adsorption and enrichment is disclosed.
The invention provides a novel pentabiphenyl macrocyclic compound aiming at the practical problem that radioiodine threatens human health and the realistic demand that excellent iodine adsorbent is still not much, the compound has a supramolecular macrocyclic main body and a bromine side chain, the supramolecular macrocyclic main body has unique cavity structure and bonding capacity, the modification of the bromine side chain provides a reaction site, and the difficulty of modifying the macrocyclic compound is greatly reduced. The macrocyclic compound can be bonded with iodine through pi-pi conjugation by utilizing an electron-rich cavity of the macrocyclic compound, is used for adsorption and enrichment of iodine, can realize high-efficiency adsorption of iodine in various solvents (including water and air), can realize high-efficiency adsorption of low-concentration iodine in water within 1 hour, has an adsorption amount of 1.1g/g in air within 14 hours, can release adsorbed iodine in cyclohexane after adsorption of the pentabiphenyl macrocyclic compound, has important theoretical significance and application value in application of iodine enrichment, has a simple synthesis method, and can only economically synthesize the pentabiphenyl by using the macrocyclic method provided by the invention.
Drawings
FIG. 1 is a graph of the adsorption of pentabiphenyl macrocycles in water for low concentrations of iodine;
FIG. 2 is a graph of the color change of pentabiphenyl macrocycles adsorbing iodine in air;
FIG. 3 is a graph of the change of the loading of pentabiphenyl macrocycles in air for adsorption of iodine versus adsorption time;
FIG. 4 is a graph of the color change of pentabiphenyl macrocycles after adsorption of iodine releasing iodine in cyclohexane solutions.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
A pentabiphenyl macrocyclic compound having the structure shown in formula (I):
a preparation method of the pentabiphenyl macrocyclic compound comprises the following specific steps: removing methyl from a pentabiphenyl methoxyl monomer compound to obtain a pentabiphenyl full-hydroxyl monomer compound, modifying the pentabiphenyl full-hydroxyl monomer compound to obtain a pentabiphenyl bromine chain monomer compound, and then placing the pentabiphenyl bromine chain monomer compound in an organic solvent to react with paraformaldehyde under the catalysis of a catalyst to obtain the pentabiphenyl macrocyclic compound.
The preparation method specifically comprises the following steps (wherein the raw materials used are commercially available as such unless otherwise specified):
(a) Dissolving a pentabiphenyl methoxyl monomer compound and boron tribromide in an organic solvent, reacting, and carrying out post-treatment to obtain a pentabiphenyl total hydroxyl monomer compound shown in a formula (II),
(b) Dissolving the pentabiphenyl full-hydroxy monomer compound obtained in the step (a), 1, 3-dibromopropane and cesium carbonate in an organic solvent, reacting, and carrying out post-treatment to obtain a pentabiphenyl bromine chain monomer compound shown in a formula (III),
(c) And (c) dissolving the pentabiphenyl bromochain monomer compound obtained in the step (b) and paraformaldehyde in an organic solvent, adding a catalyst, reacting, and performing aftertreatment to obtain the pentabiphenyl macrocyclic compound.
In step (a), the reaction is carried out in N 2 Under protection, the reaction temperature is 20-30 ℃, and the reaction time is 30-48h. The organic solvent adopts dichloromethane, and the post-treatment process specifically comprises the following steps: and (3) quenching the reaction liquid after the reaction by ice water, wherein the adding amount ratio of the pentabiphenyl methoxyl monomer compound to the boron tribromide to the organic solvent is (0.5-1.5) g, (2.0-3.0) mL and (250-350) mL.
In step (b), reacting at N 2 The reaction is carried out under protection, the reaction temperature is 80-100 ℃, and the reaction time is 10-14h. The organic solvent adopts acetonitrile, and the post-treatment process specifically comprises the following steps: naturally cooling the reaction liquid after reaction to room temperature, then carrying out suction filtration to obtain filtrate, washing a filter cake obtained by suction filtration for multiple times by using dichloromethane, combining the obtained washing liquid and the filtrate, and purifying the filtrate by adopting a silica gel column chromatography, wherein the adding amount ratio of the pentabiphenyl full-hydroxy monomer compound to the 1, 3-dibromopropane to the cesium carbonate to the organic solvent is (0.5-1.5) g, (8-10) g, (3-4) g and (200-300) mL.
In the step (c), the reaction temperature is 20-30 ℃, and the reaction time is 20-40min. The organic solvent adopts halogenated hydrocarbon, wherein the halogenated hydrocarbon is selected from one of dichloromethane, dibromomethane, trichloromethane, tribromomethane, carbon tetrachloride, dichloroethane, dibromoethane, trichloroethane, dibromoethane, tetrachloroethane, tetrabromoethane, monochloropropane, monobromopropane, monochlorobutane, monobromobutane, monochloropentane, monobromopentane, monochlorohexane, monobromohexane, monochloroheptane, monobromoheptane, monochlorooctane, monobromooctane, monochloronane, monobromonane, monochlorodecane or monobromodecane, the catalyst adopts Lewis acid, the Lewis acid adopts trifluoromethanesulfonic acid, and the post-treatment process is as follows: quenching the reaction liquid after reaction by adopting a saturated sodium bicarbonate solution, purifying the reaction liquid by adopting a silica gel column chromatography after washing, wherein the adding amount ratio of the pentabiphenyl bromine chain monomer compound to the paraformaldehyde to the organic solvent is (0.5-1.5) g, (0.060-0.070) g, (250-350) mL.
The application of the pentabiphenyl macrocyclic compound in radioactive iodine adsorption and enrichment is disclosed.
Example 1
A penta-biphenyl macrocyclic compound is prepared by the following preparation steps, including the synthesis of a penta-biphenyl full-hydroxy monomer compound in step 1; step 2, synthesizing a pentabiphenyl bromine chain monomer compound; and 3, synthesizing the pentabiphenyl macrocyclic compound.
Step 1 the synthesis equation of the pentabiphenyl total hydroxyl monomer compound is as follows:
1g (2 mmol) of a pentabiphenyl methoxyl monomer compound (synthesized according to a patent with the application number of CN 201910975631.8) is added into a 500mL round-bottom flask, and the structure of the pentabiphenyl methoxyl monomer compound is as follows:
and is poured into300mL of methylene chloride as an organic solvent, 2.4mL (24 mmol) of boron tribromide was added dropwise to the reaction solution with stirring, and N was added dropwise 2 Stirring overnight under protection, the reaction temperature is 25 ℃, ice water is added into the mixture after the reaction is finished, and the mixture is quenched to obtain a purple solid product, namely the pentabiphenyl full-hydroxy monomer compound, the yield is 80 percent, and the hydrogen spectrum data of the product is 1 H NMR(400MHz,DMSO-d6)δ9.47(s,2H),9.38(s,2H),8.02–7.41(m,8H),7.12(d,J＝8.3Hz,4H),6.43(d,J＝2.4Hz,4H),6.33(dd,J＝8.3,2.4Hz,2H).
1g (2 mmol) of a pentabiphenyl total hydroxyl monomer compound and 9g (24 mmol) of 1, 3-dibromopropane, 3.6g (8 mmol) of cesium carbonate are placed in a 500mL round-bottomed flask, 250mL of acetonitrile is poured as an organic solvent, the mixture is heated to 90 ℃ and N is added 2 Stirring and refluxing for 12h under protection, monitoring a reaction point plate, naturally cooling to room temperature after the reaction is finished, performing suction filtration, washing a filter cake for 3 times by using dichloromethane, combining filtrates, purifying a product by using a silica gel column chromatography, and using dichloromethane/petroleum ether (1/1, v/v) as eluent to obtain a white solid product, namely the pentabiphenyl bromine chain monomer compound, wherein the yield is 50%, and the hydrogen spectrum data of the product is that 1 H NMR(400MHz,CDCl 3 )δ7.67(d,J＝8.4Hz,4H),δ7.61(d,4H),7.56(d,J＝8.4Hz,4H),7.32(d,J＝8.9Hz,2H),6.61(d,J＝6.9Hz,4H),4.18(t,J＝5.8Hz,4H),4.12(t,J＝5.7Hz,4H),3.63(t,J＝6.4Hz,4H),3.52(t,J＝6.3Hz,4H),2.39-2.32(m,4H),2.31-2.22(m,4H).
Step III step 3 the synthesis equation for the pentabiphenyl macrocycles is as follows:
1g (1.05 mmol) of pentabiphenyl bromochain monomer compound and 0.064g (2.1 mmol) of paraformaldehyde are added into a 500mL round-bottom flask, and 300mL of 1, 2-dichloroethane is poured as an organic solventWhile stirring, triflic acid was added as catalyst and the reaction was monitored at 25 ℃ on a plate. And after the reaction is finished for 30 minutes, transferring the reaction solution into a 500mL separating funnel, adding 100mL saturated sodium bicarbonate solution, shaking, quenching, washing the organic layer twice with saturated sodium carbonate solution, purifying the product by silica gel column chromatography, and eluting with dichloromethane/petroleum ether (3/1, v/v) to obtain the pentabiphenyl macrocyclic compound, wherein the yield is 95%, and almost no by-product is generated. The product has hydrogen spectrum data of 1 H NMR(400MHz,CDCl 3 )δ7.61(d,J＝8.3Hz,12H),7.56(d,J＝8.3Hz,12H),7.50(d,J＝8.3Hz,12H),7.05(s,6H),6.61(s,6H),4.18–4.10(m,24H),3.94(s,6H),3.53–3.42(m,24H),2.35–2.21(m,24H).
Example 2
This example also provides the use of pentabiphenyl macrocycles for radioiodination and enrichment.
As shown in fig. 1, when the solid pentabiphenyl macrocyclic compound is immersed in an aqueous solution containing iodine elementary substance (the content of iodine elementary substance is 0.3 g/L), it can be clearly seen that, as the adsorption time is prolonged, the solution gradually changes from initial yellow to colorless, and the color of the pentabiphenyl macrocyclic compound is obviously deepened, and reaches an equilibrium after 30min, which shows that the pentabiphenyl macrocyclic compound can efficiently and rapidly adsorb and enrich iodine in water (since the adsorption amount of the pentabiphenyl macrocyclic compound to iodine in water cannot be accurately measured after water absorption, the adsorption amount of the pentabiphenyl macrocyclic compound to adsorb gaseous iodine molecules is taken as the adsorption amount of the pentabiphenyl macrocyclic compound to iodine molecules, which is specifically shown in fig. 2). As shown in fig. 2, when the pentabiphenyl macrocycle is exposed to iodine molecule vapor, the color of the solid pentabiphenyl macrocycle after adsorption of iodine molecules is also obviously deepened with the increase of adsorption time. A curve diagram of the change of the adsorption capacity of the pentabiphenyl macrocyclic compound in the air along with the time is further made. By calculating the mass percent increase of the pentabiphenyl macrocycle (calculated as W) t ＝(W T -W 1 )/W 1 ，W T For the mass of pentabiphenyl macrocycles at various time periods after iodine adsorption, W 1 For the mass of the pro-iodopentabiphenyl macrocycle) an adsorption curve as shown in figure 3 was obtained (ordinate, i.e. the mass of the pentabiphenyl macrocycle)Increased mass percent for the pentabiphenyl macrocycle), it was found that after 14 hours, 1.1g of iodine can be adsorbed per gram of the pentabiphenyl macrocycle (the ordinate represents mass percent, i.e., how many grams of iodine are adsorbed per gram of the pentabiphenyl macrocycle), exhibiting superior adsorption capacity.
As shown in fig. 4, by placing the pentabiphenyl macrocycle with adsorbed iodine in cyclohexane solution, it is clearly seen that the colorless and transparent cyclohexane solution slowly turned deep purple with time and became darker and darker, indicating that the trapped iodine was released.
Example 3
Study on the yield of the pentabiphenyl bromo-chain monomer compound, the pentabiphenyl bromo-chain monomer compound was obtained by the following preparation steps (wherein, the pentabiphenyl all-hydroxy monomer compound was obtained by the same method as in example 1):
a500 mL round-bottom flask was charged with 1g (2 mmol) of a pentabiphenyl total hydroxy monomer compound and 4.5g (12 mmol) of 1, 3-dibromopropane, 3.6g (8 mmol) of cesium carbonate, and then 250mL of acetonitrile as an organic solvent was poured, heated to 90 ℃ and N was 2 Stirring and refluxing for 12h under protection, monitoring a reaction point plate, naturally cooling to room temperature after the reaction is finished, performing suction filtration, washing a filter cake for 3 times by using dichloromethane, combining filtrates, purifying a product by using a silica gel column chromatography, and using dichloromethane/petroleum ether (1/1, v/v) as eluent to obtain a white solid product, namely the pentabiphenyl bromine chain monomer compound with the yield of 30%.
Or adding 1g (2 mmol) of pentabiphenyl total hydroxyl monomer compound and 13.5g (36 mmol) of 1, 3-dibromopropane and 3.6g (8 mmol) of cesium carbonate into a 500mL round-bottom flask, pouring 250mL of acetonitrile as an organic solvent, heating to 90 ℃, and adding N 2 Stirring and refluxing for 12h under protection, monitoring a reaction point plate, naturally cooling to room temperature after the reaction is finished, performing suction filtration, washing a filter cake for 3 times by using dichloromethane, combining filtrates, purifying a product by using a silica gel column chromatography, and using dichloromethane/petroleum ether (1/1, v/v) as eluent to obtain a white solid product, namely the pentabiphenyl bromine chain monomer compound with the yield of 50%.
As compared with example 1, it was found that the addition of excessive 1, 3-dibromopropane did not result in an increase in the yield, whereas insufficient 1, 3-dibromopropane resulted in incomplete reaction and a decrease in the yield.
Example 4
Study on yield of pentabiphenyl macrocyclic compound, the pentabiphenyl macrocyclic compound was obtained by the following preparation procedure (wherein, the pentabiphenyl bromochain monomer compound was obtained by the same method as in example 1):
a500 mL round bottom flask was charged with 1g (1.05 mmol) of pentabiphenyl bromochain monomer compound and 0.032g (1.05 mmol) of paraformaldehyde, and 300mL of 1, 2-dichloroethane as an organic solvent was poured, while stirring, trifluoromethanesulfonic acid as a catalyst was added, and the reaction was monitored by a plate at a temperature of 25 ℃. After 15 hours the reaction was complete, giving a yield of 83%.
A500 mL round bottom flask was charged with 1g (1.05 mmol) of pentabiphenyl bromochain monomer compound and 0.128g (4.2 mmol) of paraformaldehyde, and 300mL of 1, 2-dichloroethane as an organic solvent was poured, while stirring, trifluoromethanesulfonic acid as a catalyst was added, and the reaction was monitored by a plate at a temperature of 25 ℃. After 5 minutes the reaction was complete and the yield was 63%.
In comparison with example 1, the following results were obtained: too little paraformaldehyde will result in too low a yield and reaction rate, and too much paraformaldehyde will result in a much higher reaction rate but too low a yield.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A pentabiphenyl macrocyclic compound having the structure shown in formula (i):
2. a process for the preparation of a pentabiphenyl macrocycle as claimed in claim 1, wherein said process comprises: removing methyl from a pentabiphenyl methoxyl monomer compound to obtain a pentabiphenyl full-hydroxyl monomer compound, modifying the pentabiphenyl full-hydroxyl monomer compound to obtain a pentabiphenyl bromine chain monomer compound, and then placing the pentabiphenyl bromine chain monomer compound in an organic solvent to react with paraformaldehyde under the catalysis of a catalyst to obtain the pentabiphenyl macrocyclic compound.
3. The method of claim 2, wherein the method specifically comprises the steps of:
(a) Dissolving a pentabiphenyl methoxyl monomer compound and boron tribromide in an organic solvent, reacting, and carrying out post-treatment to obtain a pentabiphenyl full-hydroxyl monomer compound shown in a formula (II),
(b) Dissolving the pentabiphenyl full-hydroxy monomer compound obtained in the step (a), 1, 3-dibromopropane and cesium carbonate in an organic solvent, reacting, and carrying out post-treatment to obtain a pentabiphenyl bromine chain monomer compound shown in a formula (III),
(c) And (c) dissolving the pentabiphenyl bromochain monomer compound obtained in the step (b) and paraformaldehyde in an organic solvent, adding a catalyst, reacting, and performing aftertreatment to obtain the pentabiphenyl macrocyclic compound.
4. The method of claim 3, wherein in step (a), the reaction is carried out under N 2 The reaction is carried out under protection, and the reaction temperature is 20-30 DEG CThe reaction time is 30-48h.
5. The method for preparing a penta-biphenyl macrocyclic compound according to claim 3, wherein the organic solvent is dichloromethane, and the post-treatment process comprises: and quenching the reacted reaction solution by ice water.
6. The method of claim 3, wherein in step (b), the reaction is carried out under N 2 Under protection, the reaction temperature is 80-100 ℃, and the reaction time is 10-14h.
7. The method for preparing pentabiphenyl macrocycle according to claim 3, wherein the organic solvent is acetonitrile, and the post-treatment process is specifically: naturally cooling the reaction solution after reaction to room temperature, then carrying out suction filtration to obtain filtrate, and purifying the filtrate by adopting a silica gel column chromatography.
8. The method of claim 3, wherein the reaction temperature in step (c) is 20-30 ℃ and the reaction time is 20-40min.
9. The method for preparing a penta-biphenyl macrocyclic compound according to claim 3, wherein the organic solvent adopts halogenated hydrocarbon, the catalyst adopts Lewis acid, and the post-treatment process specifically comprises: quenching the reacted reaction solution by adopting a saturated sodium bicarbonate solution, and purifying the reaction solution by adopting a silica gel column chromatography after washing.
10. Use of a pentabiphenyl macrocycle of claim 1 for radioiodination and enrichment.
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| CN109608636A (en) * | 2018-12-13 | 2019-04-12 | 上海应用技术大学 | Rich in heteroatomic triazine radical cup [4] aromatic polymer, preparation method and applications |
| CN109705049A (en) * | 2018-12-29 | 2019-05-03 | 青岛科技大学 | A kind of preparation method and purposes of the schiff bases cyclic compound applied to the absorption of efficient iodine |
| CN110642684A (en) * | 2019-10-15 | 2020-01-03 | 天津师范大学 | Macrocyclic and cage-shaped molecules based on biphenyl arene and derivative compounds thereof, and synthetic method and application thereof |
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| CN109608636A (en) * | 2018-12-13 | 2019-04-12 | 上海应用技术大学 | Rich in heteroatomic triazine radical cup [4] aromatic polymer, preparation method and applications |
| CN109705049A (en) * | 2018-12-29 | 2019-05-03 | 青岛科技大学 | A kind of preparation method and purposes of the schiff bases cyclic compound applied to the absorption of efficient iodine |
| CN110642684A (en) * | 2019-10-15 | 2020-01-03 | 天津师范大学 | Macrocyclic and cage-shaped molecules based on biphenyl arene and derivative compounds thereof, and synthetic method and application thereof |
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