CN105130950A - Bisamide-substituted novel calixcrown ether compound as well as synthesis method and application thereof - Google Patents

Abstract

The present invention relates to a novel calixarene crown ether compound substituted by bisamide, the general chemical formula of which is 11,23-bis(amido)-25,27-bis(2-propoxy)-calix[4]arene- Crown-6; Its synthetic method is to first synthesize 11,23-bis(amino)-25,27-bis(2-propoxy)-calix [4]arene-crown-6 intermediate, and the intermediate is condensed with acid chloride have to. The synthetic 11,23-bis(amido) 25,27-bis(2-propoxy)-calix[4]arene-crown-6 can not only increase the extraction capacity of the extractant by increasing the length of the amido carbon chain Hydrophobic, and the calixarene crown ether compound after introducing the amide group, under the same extraction conditions, the extraction distribution ratio of cesium is at least 5 times higher, and the improvement of extraction performance reduces the level of the extractor during the extraction process. The number reduces the separation cost and is expected to be applied to the removal of cesium ions in radioactive wastewater.

Description

Novel calixarene crown ether compound substituted by bisamide and its synthesis method and application

technical field

The invention belongs to the technical field of organic extractants, in particular to a novel calixarene crown ether compound substituted by bisamides and its synthesis method and application. The novel calixarene crown ether compound is 11,23-bis(amido)-25, 27-Bis(2-propoxy)-calix[4]arene-crown-6.

Background technique

Cesium-137 is one of the long-lived fragment nuclides produced in the process of nuclear fuel fission. It mainly exists in the high-level waste liquid produced by the reprocessing of spent fuel, and has the characteristics of high heat release rate and strong radioactivity. If it is separated from the high-level waste liquid, it will not only help reduce the radioactive intensity of the high-level waste liquid, but also reduce the volume of vitrification, thereby greatly reducing the disposal cost of the high-level waste liquid. Therefore, the development of cesium-137 separation technology is in line with the needs of the advanced fuel cycle strategy and is also a prerequisite for the sustainable development of nuclear energy.

At present, the methods for separating cesium under strong acid conditions mainly include precipitation method, ion exchange method, membrane separation method and solvent extraction method. Among them, the solvent extraction method is considered to be the most promising for the separation of cesium in high-level waste liquid due to its advantages of high selectivity, good separation effect, simple equipment, and convenient operation.

Calixarene crown ethers have a strong complexation effect on alkali metals and alkaline earth metals, and have been widely used in solvent extraction, liquid membrane separation and ion selective electrodes. The strength of its complexation with metal depends on the number of oxygen atoms, the length of the crown ether bridge and the three-dimensional structure of calixarene. Among them, the 1,3-alternating conformation of diisopropoxycalix[4]arene-crown-6 was proved to have a strong coordination ability with cesium ions. During the coordination process, cesium ions not only react with the 6 oxygen atoms on the crown ether ring, but also conjugate with the π-electrons of the aromatic ring on the calixarene. Although 25,27-bis(2-propoxy)-calix[4]arene-crown-6 with 1,3 alternating conformation has good extraction performance for cesium under acidic conditions, the distribution of cesium is relatively low, and Its fat solubility is not good, and the distribution ratio in common diluents such as chloroform and xylene is not high. By changing the chemical environment of the aromatic ring in calixarene, not only the above problems can be overcome, but also the extraction distribution ratio of calix[4]arene-crown-6 to cesium is expected to be improved.

Contents of the invention

Aiming at the deficiencies of the prior art, the present invention provides a novel calixarene crown ether compound substituted with bisamide, including its synthesis method and application.

A novel calixarene crown ether compound substituted by a bisamide, whose general chemical formula is 11,23-bis(amido)-25,27-bis(2-propoxyl)-calix[4]-crown-6, Its structural general formula is as follows:

Wherein R is (CH ₂ ) _n CH ₃ , n=0-7.

A method for preparing a novel calixarene crown ether compound substituted by bisamides as described above mainly comprises the following steps:

1) Synthesis of 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6

Add 25,27-bis(isopropoxy)calix[4]arene-crown-6 and acetic anhydride with a molar ratio of 1:(200~400) into the reaction vessel, cool to 5~-15°C, stir 0.5~1h, then slowly add the mixture of acetic anhydride, acetic acid and concentrated nitric acid with a volume ratio of (50~100):(40~100):1 to the above system, and continue to stir for 2~5h after the addition , raised to room temperature, stirred at room temperature for 12-24h, then poured into an ice-water mixture, stirred until all solids were precipitated, filtered with suction, dried to obtain a crude product, and used a volume ratio of (2-4):1 A mixed solvent of methanol and ether was recrystallized to obtain a light yellow powder solid, namely 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 ;

2) Synthesis of 11,23-bis(amino)-25,27-bis(2-propoxy)-calix[4]arene-crown-6

Add 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 and ethanol with a molar ratio of 1:(1200~1600) into the reaction vessel In, protect with nitrogen, and add palladium carbon catalyst and hydrazine hydrate, wherein palladium carbon catalyst and 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene- The mass ratio of crown-6 is 1:(10～20), 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 and hydrazine hydrate The molar ratio is 1:(100~200). After the dropwise addition, pass nitrogen gas for protection, heat to 80°C, and reflux for 0.5~5h. After the reaction, cool to room temperature, remove the solid catalyst by suction filtration, and decompress the filtrate Rotary steaming, the obtained crude product was recrystallized to obtain white flaky crystals, which was the product 11,23-bis(amino)-25,27-bis(2-propoxy)-calix[4]arene-crown -6;

3) Synthesis of 11,23-bis(amido)-25,27-bis(2-propoxy)-calix[4]arene-crown-6

Add 11,23-bis(amino)-25,27-bis(2-propoxyl)-calix[4arene]-crown-6 and dichloromethane solution with a molar ratio of 1:(200～500) to In the reaction vessel, protect it with nitrogen gas, and cool the mixture to 5~-5°C, then add acid chloride (CH ₃ (CH ₂ ) _n C(=O)Cl, n=0-7) and triethylamine , wherein the molar ratio of acid chloride, triethylamine and 11,23-bis(amino)-25,27-bis(2-propoxyl)-calix[4]arene-crown-6 is (2～5 ): (2～4): 1. After the dropwise addition, warm up to room temperature, stir, and heat to reflux for 1～3h. After the reaction, the reaction solution is directly decompressed and spin-dried, and the obtained crude product is dissolved with an organic solvent. And wash with distilled water, collect the organic phase, dry, suction filter, spin the filtrate to dry, add a small amount of organic solvent to dissolve, drop into petroleum ether to obtain a white precipitate, filter and dry to obtain the product 11,23-bis(amido)25, 27-Bis(2-propoxy)-calix[4]arene-crown-6.

Wherein, the organic solvent described in step 3) is dichloromethane, chloroform or carbon tetrachloride.

The drying of the organic phase described in step 3) uses anhydrous sodium sulfate, silica gel, activated alumina or molecular sieves.

As mentioned above, the application of a novel calixarene crown ether compound substituted by bisamides in the extraction of cesium.

The application is the extraction of cesium from an aqueous solution containing cesium.

The nitric acid concentration _CHNO3 in the cesium-containing aqueous solution is 0˜6 mol/L.

The novel calixarene crown ether substituted by bisamide is diluted with a diluent as an extractant, and the diluent is selected from one or more of chloroform, dichloromethane and ethyl acetate.

The temperature of the extraction reaction was 25°C.

The beneficial effects of the present invention are: the present invention synthesizes amide-substituted calix[4]arene-crown-6 derivatives through a three-step reaction, and provides a new method for the construction and synthesis of novel calixarene crown ether extractants train of thought. The method of the invention controls the reaction temperature to be relatively low, avoids the generation of many by-products in the reaction process, and at the same time, the reaction efficiency of the whole synthesis process is high, the purification process is simple, and the purity of the product can be guaranteed to be >95% without column separation. In addition, the 11,23-bis(amido)25,27-bis(2-propoxy)-calix[4]arene-crown-6 synthesized by the present invention can not only increase the extraction by increasing the length of the amido carbon chain The hydrophobicity of the agent, and the introduced amide group can promote the extraction of cesium by calixarene crown ether under acidic conditions to a certain extent. Taking the obtained 11,23-bis(propionamido)25,27-bis(2-propoxyl)-calix[4]arene-crown-6 as an example, its extraction of cesium in chloroform is relatively Compared with unmodified 25,27-bis(2-propoxy)-calix[4]arene-crown-6, under the same extraction conditions, the extraction distribution ratio was at least 5 times higher, and the extraction performance The improvement reduces the number of stages of the centrifugal extractor in the extraction process, reduces the separation cost, and is expected to be applied to the removal of cesium ions in radioactive wastewater.

Description of drawings

Fig. 1 is a kind of novel calixarene crown ether of the present invention 11,23-bis(propionamido)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 to the extraction distribution of cesium The graph of the change of ratio D with the nitric acid concentration _CHNO3 .

Detailed ways

The following _{11,23 -} bis(amido)25,27-bis( ₂ The synthesis of -propoxy)-calix[4]arene-crown-6 is taken as an example, and the present invention is illustrated in conjunction with specific examples.

Example 1 11,23-bis(propionamido)-25,27-bis(2-propoxy)-calix[4]arene-crown-6

1) Synthesis of 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6: 4.26 g of 25,27 in alternate conformation of 1,3 -Bis(2-propoxy)-calix[4]arene-crown-6 was dissolved in 150mL of acetic anhydride, cooled to -10°C, stirred for 30min, and a mixture consisting of 100mL of acetic anhydride, 100mL of acetic acid and 1mL of concentrated nitric acid was Slowly add it dropwise to the above system, continue to stir for 3 hours after the drop is completed, rise to room temperature, and stir for 12 hours. The reaction solution was poured into 500mL of ice-water mixture, stirred until solid precipitation was complete, suction filtered, and dried. The obtained crude product was recrystallized with a mixed solvent of methanol and ether with a volume ratio of 5:2 to obtain a light yellow powder solid. That is, 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6, yield=93%;

2) Synthesis of 11,23-bis(amino)-25,27-bis(2-propoxy)-calix[4]arene-crown-6: Take 0.8g of the above product and add it to 80mL of ethanol, blow nitrogen, Add 0.05g palladium carbon catalyst, then add 10mL hydrazine hydrate with a mass fraction of 80%, heat to 80°C, stop heating after reflux for 3h, cool to room temperature, remove the catalyst by suction filtration, take the filtrate and spin evaporate under reduced pressure to obtain the crude product Recrystallize with ethanol to obtain white flaky crystals, which is the product 11,23-bis(amino)-25,27-bis(2-propoxyl)-calix[4]arene-crown-6; yield = 87%;

3) Synthesis of 11,23-bis(propionamido)25,27-bis(2-propoxy)-calix[4]arene-crown-6: Add 0.740 g of the obtained white flaky crystals to 20 mL of bis Dissolve in methyl chloride, blow nitrogen, cool to 0°C, add 0.20g propionyl chloride, dropwise add 0.25g triethylamine, after the drop is completed, raise to room temperature, stir, and heat to reflux for 2h. After the reaction, the reaction solution was directly spin-dried under reduced pressure, dissolved in dichloromethane, and washed three times with distilled water, the organic phase was collected, dried with anhydrous sodium sulfate, filtered with suction, the filtrate was spin-dried, and dissolved in a small amount of dichloromethane , drop into petroleum ether to obtain a white precipitate, filter and dry to obtain the product 11,23-bis(propionamido)25,27-bis(2-propoxyl)-calix[4]arene-crown-6, the yield was 81%.

Dissolve the extractant 11,23-bis(propionamido)25,27-bis(2-propoxy)-calix[4]arene-crown-6 in chloroform to prepare a concentration of 0.01mol/L The concentration of cesium ions in the cesium-containing aqueous solution is 0.3g/L, and the concentration of nitric acid is 0.1mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L respectively. Take equal volumes of the aqueous phase and the organic phase in 10mL centrifuge test tubes, shake in a constant temperature water bath at 25°C for 60 minutes under atmospheric pressure, centrifuge and separate the layers, and detect the concentration of cesium ions in the aqueous phase. The extraction rate of cesium is above 90%; the concentration of cesium ions in the organic phase is calculated by subtraction method, and then the distribution ratio is obtained according to the concentration ratio of cesium ions in the two phases. As shown in Figure 1 and Table 1, when _CHNO3 = 3 mol/L, the distribution ratio can reach up to 67, and when _CHNO3 = 5 mol/L, the distribution ratio still reaches 22.9.

Table 1 Extraction data under different nitric acid concentrations

Example 2 11,23-bis(propionamido)-25,27-bis(2-propoxy)-calix[4]arene-crown-6

The method for synthesizing white flaky crystal 11,23-bis(amino)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 is the same as that in Example 1.

Add 0.740 g of the obtained white flaky crystals into 20 mL of dichloromethane to dissolve, blow nitrogen, cool to -5°C, add 0.25 g of propionyl chloride, dropwise add 0.3 g of triethylamine, and heat to reflux for 3 h after the drop is completed. After the reaction, the reaction solution was directly spin-dried under reduced pressure, dissolved in dichloromethane, and washed three times with distilled water, the organic phases were combined, dried with sodium sulfate, filtered with suction, the filtrate was spin-dried, dissolved in a small amount of dichloromethane, and dropped Add white precipitate to petroleum ether, filter and dry to obtain the product 11,23-bis(propionamido)25,27-bis(2-propoxy)-calix[4]arene-crown-6.

Example 3 11,23-bis(butyramide) 25,27-bis(2-propoxy)-calix[4]arene-crown-6

1) Synthesis of 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6: 4.26 g of 25,27 in alternate conformation of 1,3 -Bis(2-propoxy)-calix[4]arene-crown-6 was dissolved in 150mL of acetic anhydride, cooled to -15°C, stirred for 30min, and a mixture consisting of 100mL of acetic anhydride, 100mL of acetic acid and 1mL of concentrated nitric acid was Slowly add it dropwise to the above system, continue to stir for 3 hours after the drop is completed, rise to room temperature, and stir for 12 hours. The reaction solution was poured into 500 mL of ice-water mixture, stirred until solid precipitation was complete, suction filtered, and dried. The obtained crude product was recrystallized with a mixed solvent of methanol and ether with a volume ratio of 5:2 to obtain a light yellow solid.

2) Synthesis of 11,23-bis(amino)-25,27-bis(2-propoxy)-calix[4]arene-crown-6: Take 0.8g of the above product and add it to 80mL of ethanol, blow nitrogen, Add 0.05g of palladium-carbon catalyst, then add 8mL of hydrazine hydrate, heat to 80°C, reflux for 1 hour, stop heating, remove the catalyst by suction filtration, take the filtrate and rotary evaporate under reduced pressure, and recrystallize the obtained crude product with ethanol to obtain a white flake The crystal is the product 11,23-bis(amino)-25,27-bis(2-propoxy)-calix[4]arene-crown-6.

3) Synthesis of 11,23-bis(butanylamino)25,27-bis(2-propoxy)-calix[4]arene-crown-6: Add 0.740 g of the obtained white flaky crystals to 30 mL di Methane chloride was dissolved, blown with nitrogen, cooled to 0°C, added 0.25g of butyryl chloride, and 0.25g of triethylamine was added dropwise, and heated to reflux for 2h after the drop was completed. After the reaction, the reaction solution was directly spin-dried under reduced pressure, dissolved in dichloromethane, and washed three times with distilled water, the organic phase was combined, dried with anhydrous sodium sulfate, filtered with suction, the filtrate was spin-dried, and dissolved in a small amount of dichloromethane , drop into petroleum ether to obtain a white precipitate, filter and dry to obtain the product 11,23-bis(butyrylamide) 25,27-bis(2-propoxyl)-calix[4]arene-crown-6, the yield = 80%.

Example 4 11,23-bis(octylamino)25,27-bis(2-propoxy)-calix[4]arene-crown-6

The method for synthesizing white flaky crystal 11,23-bis(amino)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 is the same as that in Example 3.

Add 0.740 g of the obtained white flaky crystals into 30 mL of dichloromethane to dissolve, blow nitrogen gas, cool to -5°C, add 0.5 g of octanoyl chloride, add dropwise 0.3 g of triethylamine, and heat to reflux for 3 hours after the drop is completed. After the reaction, the reaction solution was directly spin-dried under reduced pressure, dissolved in dichloromethane, and washed three times with distilled water, the organic phase was combined, dried with anhydrous sodium sulfate, filtered with suction, the filtrate was spin-dried, and dissolved in a small amount of dichloromethane , drop into petroleum ether to obtain a white precipitate, filter and dry to obtain the product 11,23-bis(octylamido)25,27-bis(2-propoxyl)-calix[4]arene-crown-6, the yield = 84%.

Claims (9)

1. a novel calixarene crown ether compound substituted by two amides, characterized in that its general chemical formula is 11,23-two (amido)-25,27-two (2-propoxy)-calix[4 ]-crown-6, its structural general formula is as follows: Wherein R is (CH ₂ ) _n CH ₃ , n=0-7. 2. the preparation method of the novel calixarene crown ether compound of a kind of bisamide substitution as claimed in claim 1, is characterized in that, mainly comprises the following steps: 1) Synthesis of 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 Add 25,27-bis(isopropoxy)calix[4]arene-crown-6 and acetic anhydride with a molar ratio of 1:(200~400) into the reaction vessel, cool to 5~-15°C, stir 0.5~1h, then slowly add the mixture of acetic anhydride, acetic acid and concentrated nitric acid with a volume ratio of (50~100):(40~100):1 to the above system, and continue to stir for 2~5h after the addition , raised to room temperature, stirred at room temperature for 12-24h, then poured into an ice-water mixture, stirred until all solids were precipitated, filtered with suction, dried to obtain a crude product, and used a volume ratio of (2-4):1 A mixed solvent of methanol and ether was recrystallized to obtain a light yellow powder solid, namely 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 ; 2) Synthesis of 11,23-bis(amino)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 Add 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 and ethanol with a molar ratio of 1:(1200~1600) into the reaction vessel In, protect with nitrogen, and add palladium carbon catalyst and hydrazine hydrate, wherein palladium carbon catalyst and 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene- The mass ratio of crown-6 is 1:(10～20), 11,23-bis(nitro)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 and hydrazine hydrate The molar ratio is 1:(100~200). After the dropwise addition, pass nitrogen gas for protection, heat to 80°C, and reflux for 0.5~5h. After the reaction, cool to room temperature, remove the solid catalyst by suction filtration, and decompress the filtrate Rotary steaming, the obtained crude product was recrystallized to obtain white flaky crystals, which was the product 11,23-bis(amino)-25,27-bis(2-propoxy)-calix[4]arene-crown -6; 3) Synthesis of 11,23-bis(amido)-25,27-bis(2-propoxy)-calix[4]arene-crown-6 Add 11,23-bis(amino)-25,27-bis(2-propoxyl)-calix[4arene]-crown-6 and dichloromethane solution with a molar ratio of 1:(200～500) to In the reaction vessel, protect it with nitrogen gas, and cool the mixture to 5~-5°C, then add acid chloride (CH ₃ (CH ₂ ) _n C(=O)Cl, n=0-7) and triethylamine , wherein the molar ratio of acid chloride, triethylamine and 11,23-bis(amino)-25,27-bis(2-propoxyl)-calix[4]arene-crown-6 is (2～5 ): (2～4): 1. After the dropwise addition, warm up to room temperature, stir, and heat to reflux for 1～3h. After the reaction, the reaction solution is directly decompressed and spin-dried, and the obtained crude product is dissolved with an organic solvent. And wash with distilled water, collect the organic phase, dry, suction filter, spin the filtrate to dry, add a small amount of organic solvent to dissolve, drop into petroleum ether to obtain a white precipitate, filter and dry to obtain the product 11,23-bis(amido)25, 27-Bis(2-propoxy)-calix[4]arene-crown-6. 3. preparation method as claimed in claim 2 is characterized in that, the organic solvent described in step 3) is dichloromethane, trichloromethane or carbon tetrachloride. 4. preparation method as claimed in claim 2 is characterized in that, the drying of organic phase described in step 3) uses anhydrous sodium sulfate, silica gel, activated alumina or molecular sieve. 5. the application of a novel calixarene crown ether compound substituted by a kind of bisamide as claimed in claim 1 in extracting cesium. 6. application as claimed in claim 5, is characterized in that, this application is to extract cesium from cesium-containing aqueous solution. 7. The application according to claim 6, characterized in that the concentration of nitric acid in the cesium-containing aqueous solution _CHNO3 =0～6mol/L. 8. application as claimed in claim 5, is characterized in that, the novel calixarene crown ether that described bisamide replaces uses thinner to dilute as extraction agent, and described thinner is selected from chloroform, methylene dichloride and ethyl acetate one or more of. 9. application as claimed in claim 5, is characterized in that, the temperature of extraction reaction is 25 ℃.