Secondary amine and amide podand ether ligand containing ether bond and preparation method and application thereof
阅读说明：本技术 含醚键的仲胺、酰胺荚醚配体及其制备方法与应用 (Secondary amine and amide podand ether ligand containing ether bond and preparation method and application thereof ) 是由 丁颂东 杨秀英 宋莲君 王学羽 肖茜 徐皓威 于 2020-07-25 设计创作，主要内容包括：本发明公开了一种含醚键的仲胺、酰胺荚醚配体及其制备方法与应用,该含醚键的仲胺,其结构通式为<Image he="131" wi="700" file="DDA0002601989930000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明所提供的仲胺含有醚键,具有比单纯碳链仲胺更大的柔性,且易于延长原子个数,从而为有机合成化学和药物化学领域提供了具有优异性能的候选仲胺。以仲胺为原料制备的酰胺荚醚配体在乏燃料后处理中,将其作为镧系/锕系共萃体系的萃取剂,能够在更高的金属离子浓度或硝酸浓度下有效抑制三相的形成,因此在工业应用的酸度范围内实现良好的分离效果,因而不仅具有较强的实用性,且在先进核燃料循环领域也具有很好的应用前景。(The invention discloses a secondary amine containing ether bond, an amide podand ligand, a preparation method and application thereof The secondary amine provided by the invention contains ether bonds, has higher flexibility than the simple carbon chain secondary amine, and is easy to extend the number of atoms, so that the secondary amine candidate with excellent performance is provided for the fields of organic synthetic chemistry and pharmaceutical chemistry. In the spent fuel post-treatment, the amide podand ether ligand prepared by taking secondary amine as a raw material is used as an extractant of a lanthanide/actinide co-extraction system, and can effectively inhibit the formation of three phases under higher metal ion concentration or nitric acid concentration, so that a good separation effect is realized in the acidity range of industrial application, and the amide podand ether ligand has strong practicability and good application prospect in the field of advanced nuclear fuel circulation.)
1. A secondary amine containing an ether bond, characterized in that the structural formula of the secondary amine is as follows:
in the formula, R1、R2Straight-chain alkyl of carbon atoms 6-16, which may be the same or different, n is 0 or 1.
2. Secondary amine containing ether linkages according to claim 1, characterized in that R1、R2Is any one of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl straight-chain alkyl.
3. The method for producing a secondary amine containing an ether bond as claimed in claim 1 or 2, characterized by comprising the steps of:
(1) according to the synthesis route I, firstly, under the condition of normal temperature stirring, adding potassium carbonate, potassium iodide and alkyl halide with the structural formula (2) into a solvent I in which benzylamine is dissolved, then heating and refluxing for reaction for at least 10 hours, after the reaction is finished, performing suction filtration, rotary evaporation to remove the solvent I, and purifying to obtain a tertiary benzylamine compound with the structural formula (3); wherein the volume ratio of the amount of the benzylamine to the solvent I is 1 (2500-5000), the amount of the benzylamine is mol, the volume unit is mL, and the molar ratio of the benzylamine to the alkyl halide to the potassium carbonate to the potassium iodide is 1 (2.5-4) to (2-5) to (0.01-0.02);
in the structural formula (2), X is Cl, Br or I; if X is I, potassium iodide is not required to be added;
(2) according to a synthesis route II, under the stirring condition, adding an alkali I into a solvent II in which a tertiary benzylamine compound with a structural formula (3) is dissolved, reacting at normal temperature for 1-3 hours, and then adding R1Heating and refluxing the halogenated compound X for reaction for at least 10h, after the reaction is finished, performing suction filtration and rotary evaporation to remove the solvent II, and purifying to obtain an amine compound I with a structural formula (4); wherein the volume ratio of the substance quantity of the tertiary benzylamine compound with the structural formula (3) to the solvent II is 1 (2500-5000), the substance quantity unit is mol, the volume unit is mL, and the tertiary benzylamine compound with the structural formula (3) and R are1The molar ratio of the X halide to the alkali I is 1 (1-2) to 1-2;
(3) according to the synthesis route II, under the stirring condition, adding the amine compound I with the structural formula (4) into the solvent II in an ice-water bath at 0-10 ℃ until the amine compound I is completely dissolved, then adding the alkali II at the temperature until the surface of the solution is stable,no bubble is generated, the reaction is continued for 1 to 3 hours after the temperature is raised to the normal temperature, and then R is added2Carrying out heating reflux reaction on the halogenated compound X for at least 10h, after the reaction is finished, carrying out suction filtration and rotary evaporation to remove the solvent II, and purifying to obtain an amine compound II with the structural formula (5); wherein the volume ratio of the amine compound I with the structural formula (4) to the solvent II is 1 (2500-5000), the unit of the amount of the substance is mol, the unit of the volume is mL, and the amine compound I, R with the structural formula (4)2The molar ratio of the X halide to the alkali II is 1 (1-2) to 1-2;
(4) according to the synthesis route III, under the stirring condition, mixing an amine compound II with a structural formula (5) with a chloroformate derivative, heating and refluxing at 60-120 ℃ for 3-10 h to remove the redundant chloroformate derivative, adding methanol, continuing to heat and reflux at 40-60 ℃ for 3-5 h, removing the redundant methanol, and purifying to obtain a secondary amine with a structural formula (6); the ratio of the amount of the amine compound II with the structural formula (5) to the volume of the chloroformate derivative to the volume of the methanol is 0.05 (100-200) to (100-200), wherein the amount of the substance is mol, and the volume unit is mL;
the R is1、R2The same or different.
4. A process for producing a secondary amine containing an ether bond as claimed in claim 1 or 2, characterized by comprising the steps of:
(1) according to the synthesis route I, firstly, under the condition of normal temperature stirring, adding potassium carbonate, potassium iodide and alkyl halide with the structural formula (2) into a solvent I in which benzylamine is dissolved, then heating and refluxing for reaction for at least 10 hours, after the reaction is finished, performing suction filtration, rotary evaporation to remove the solvent I, and purifying to obtain a tertiary benzylamine compound with the structural formula (3); wherein the volume ratio of the amount of the benzylamine to the solvent I is 1 (2500-5000), the amount of the benzylamine is mol, the volume unit is mL, and the molar ratio of the benzylamine to the alkyl halide to the potassium carbonate to the potassium iodide is 1 (2.5-4) to (2-5) to (0.01-0.02);
in the structural formula (2), X is Cl, Br or I; if X is I, potassium iodide is not required to be added;
(2) according to a synthesis route IV, under the stirring condition, adding a tertiary benzylamine compound with a structural formula (3) into a solvent II in an ice-water bath at 0-10 ℃ until the tertiary benzylamine compound is completely dissolved, then adding an alkali II at the temperature, after the surface of the solution is stable and no bubbles exist, heating the obtained reaction system to normal temperature, continuing to react for 1-3 hours, adding R1Carrying out heating reflux reaction on the halogenated compound X for at least 10h, carrying out suction filtration, carrying out rotary evaporation to remove the solvent II, and purifying to obtain an amine compound III with a structural formula of (5)'; wherein the volume ratio of the substance quantity of the tertiary benzylamine compound with the structural formula (3) to the solvent II is 1 (2500-5000), the substance quantity unit is mol, the volume unit is mL, and the tertiary benzylamine compound with the structural formula (3) and R are1The molar ratio of the X halide to the alkali II is 1 (2-5) to (2-5);
(3) according to the synthesis route V, under the stirring condition, mixing an amine compound III with a structural formula (5) 'with a chloroformate derivative, heating and refluxing at 60-120 ℃ for 3-10 h to remove the redundant chloroformate derivative, adding methanol, continuing to heat and reflux at 40-60 ℃ for 3-5 h, removing the redundant methanol, and purifying to obtain a secondary amine with a structural formula (6)'; the ratio of the amount of the substance of the amine compound III with the structural formula (5)' to the volume of the chloroformate derivative to the volume of the methanol is 0.05: 100-200, the amount of the substance is mol, and the volume is mL.
5. The method for producing a secondary amine containing an ether bond according to claim 3 or 4, characterized in that the solvent I is any one of 1, 4-dioxane, acetone, butanone, dichloromethane, tetrahydrofuran, benzene, or toluene; the solvent II is any one of tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, benzene or toluene; the alkali I is at least one of sodium hydroxide, potassium carbonate, potassium hydroxide and sodium carbonate; the alkali II is at least one of sodium hydride, potassium tert-butoxide, sodium ethoxide, sodium amide, sodium isopropoxide and butyl lithium; the chloroformate derivative may be any one of ethyl chloroformate, vinyl chloroformate, 1-chloroethyl chloroformate, β -trichloroethyl chloroformate or β -trimethylsilylethyl chloroformate.
6. The method for producing a secondary amine having an ether bond according to claim 5, wherein when n is 0, the method for producing a tertiary benzylamine compound represented by the formula (3) is replaced with:
according to the synthesis route VI, under the stirring condition, adding potassium carbonate and halogenated benzyl into a solvent I in which diethanol amine is dissolved, heating and refluxing for 8-10 h, cooling the obtained reaction liquid to normal temperature, performing suction filtration on the obtained filtrate, removing the solvent I, and purifying to obtain a tertiary benzylamine compound with the structural formula (3)'; the volume ratio of the mass of the diethanol amine to the solvent I is 1 (2500-5000), the mass unit of the diethanol amine is mol, the volume unit of the diethanol amine is mL, and the molar ratio of the diethanol amine to the halobenzyl to the potassium carbonate is 1 (1-1.2) to 2-3.
7. An amide podand ligand characterized in that the ligand has the following general structural formula:
in the formula, R1、R2Straight-chain alkyl, branched-chain alkyl or cyclic alkyl of carbon atoms 8-16, which may be the same or different, n is 0 or 1.
8. A method for preparing an amide podand ligand, comprising the steps of:
(1) heating and refluxing diglycolic acid and thionyl chloride at 40-60 ℃ for reaction for 6-8 hours, distilling under reduced pressure by using a water pump, and collecting fractions at 110-130 ℃ under the vacuum degree of 0.1-0.15 MPa to obtain pale yellow oily diglycolic chloride; the volume ratio of the substances of the diglycolic acid to the thionyl chloride is 0.05: 100-200, the unit of the amount of the substances is mol, and the unit of the volume is mL;
(2) under the condition of stirring, mixing and stirring the secondary amine containing ether bonds as claimed in any one of claims 1 to 4 and an acid-binding agent in a solvent IV in a cold salt bath at the temperature of less than 5 ℃, dropwise adding diglycolic chloride into the mixed system in the stirring process, continuously reacting for 1-2 h after the dropwise adding is finished, and then heating to room temperature for reacting for at least 3 h; washing the obtained filtrate with acid solution, alkali solution and water in sequence to neutrality, and washing the organic layer with anhydrous Na2SO4Drying, filtering, removing the solvent IV and purifying to obtain the diamide podophyllum ether ligand; the molar ratio of the diglycolic chloride, the secondary amine containing ether bonds and the acid-binding agent is 1 (2-3) to 0.4-1, and the solvent IV is benzene or dichloromethane.
9. Use of an amide pod ligand prepared according to claim 8 for the separation and extraction of lanthanides from actinides.
Technical Field
The invention belongs to the technical field of intermediates, relates to a secondary amine compound intermediate in organic chemistry, and particularly relates to a secondary amine containing an ether bond, a preparation method thereof, and application thereof in an amide podophyllum ether ligand in a post-processing lanthanide actinide co-extraction system for preparing spent fuel.
Background
The amido podands are a new type of 'completely incineratable' neutral complexing extraction agent developed in recent years, and the structural general formula of the neutral complexing extraction agent is O (CH)2CON(R1R2)2)2Also known as Diglycolamide (DGA). They can effectively co-extract lanthanide and actinide ions from a nitric acid medium, in particular N, N, N ', N' -Tetracotyldlycolamide (TODGA), can directly use kerosene as a diluent, has enough extraction distribution ratio on An (III, IV, V) in the nitric acid medium, has smaller extraction distribution ratio on lobe elements (except Ln (III) and Zr (IV)), and has good irradiation stability, so that the TODGA can extract and separate Ln (III), An (III) and Zr (IV) from high-level waste liquid containing a large amount of lobe elements, and is very hopeful to be applied to the treatment of the high-level waste liquid in the nuclear industry. However, TODGA in a non-polar diluent is prone to emulsification or low third phase extraction capacity when the extraction acidity or metal ion concentration is high. The third phase is defined as: in liquid-liquid extraction, when the concentration of solute (e.g., metal-extractant complex, acid, extractant, etc.) in the organic phase exceeds a certain value, it spontaneously separates into two layers of a dense, upper light phase and a lower heavy phase, where the lower heavy phase is often referred to as the "third phase". The third phase is unfavorable for extraction, and the occurrence of the third phase must be avoided in the actual treatment process. The existing elimination is to add a significant amount of phase modifier to avoid the formation of a third phase. However, the addition of phase modifiers not only makes the organic phase more complex, but also has a certain inhibiting effect on the TODGA extraction am (III) and Ln (III). Meanwhile, Sr (II) is extracted to a certain degree, and the decontamination coefficient of An to Sr is reduced. In addition, the radiation degradation of the phase modifier also can bring adverse effect to the extraction performance of TODGA, and significantly increases the recovery and reuse burden of the extractant [ Tachimori S, Sasaki Y, Suzuki S.Solv Extr Ion Extch, 2002,20(6): 687-699; magnusson D, Christiansen B, Glatz J-P, et al, Partitioning of minor action from Purex reacting by the TODGA Processes of Global 2007, Boise, Idaho, USA, Sep.9-13,2007: 713-plus 718; modolo G, Asp H, Vijgen H, et al, Demonstrationof a TODGA/TBP Process for recovery of three activities and lanthionesfrom a Purex raffinates proceedings of Global 2007, Boise, Idaho, USA, Sep.9-13,2007: 1111-. Therefore, it is necessary to develop a new amide pod extractant without the use of phase modifiers!
It is found that alkane (such as N-dodecane, kerosene) is used as diluent, and the diluent is taken along with N atom of amideThe substituent chain length is increased, the extraction capacity of DGA is increased, and when the substituent is lauryl, TDdDGA (N, N, N ', N' -tetradodecycliglycamide) is used for extracting Ln from nitric acid solution3+Little emulsification or third phase occurs. This indicates that increasing the substituent chain length is one of the effective ways to inhibit the appearance of third phases in DGA extraction. [ Sasaki, Y.; zhu, z. -x.; sugo, y.; suzuki, h.; kimura, T.extraction capacity of diglycolamide derivatives for Ca2+,Nd3+and Zr4+from nitrile acid to n-diethyl containing a solvent modifier, analytical Chimica acta.2005,21, 1171-; sasaki, y.; sugo, y.; suzuki, s.; kimura, T.A method for the determination of extraction capacity and update to N, N, N ', N' -quaternary derivatives of diglycolamide-monoamide/N-Candida media Acta 2005,543,31-37 ] however, this method, which relies solely on increasing the length of the substituted alkyl chain, has the disadvantages of extremely difficult sources of the starting secondary amines, high cost of DGA synthesis, etc. However, the price of di-n-octylamine containing 8C is about 1000 yuan/500 mL, while the price of didecylamine containing 10C is 5.0g about 300 yuan; dilaurylamine with 12C atoms 5.0g about 500 yuan (RMB). It is found that dialkylamines containing 8 or more carbon atoms are several times or tens of times more expensive than di-n-octylamine and are not readily available. Therefore, the method of avoiding adding the phase modifier by simply increasing the chain length of the dialkylamine leads to an abnormally high cost for preparing the amide pod ether extractant, and is difficult to apply to the actual process of spent fuel post-treatment.
Therefore, it is of great practical significance to find new ways and methods to break through this limitation. The method simultaneously considers two methods of enhancing the polarity of DGA molecules and increasing the chain length of a substituent group, and designs and synthesizes a series of secondary amines containing polar ether bonds by adopting a mode of extending the chain length of an ether chain, and a novel amide podand ether ligand TROEDGA synthesized by taking the secondary amines as raw materials.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art, and provides a novel secondary amine containing ether bonds, wherein the total carbon number of the secondary amine can reach more than 8 and even 18, and the secondary amine is grafted with ether bonds, so that the flexibility of the secondary amine can be improved.
The invention provides a method for preparing the secondary amine containing the ether bond, and the method has mild preparation conditions, simple operation and easy control.
Still another object of the present invention is to provide an amide podand ligand prepared from the above secondary amine containing an ether bond as a raw material.
It is a further object of the present invention to provide a process for the preparation of the above described amide podophyllum ligands.
A fifth object of the invention is to provide the use of the above described amide pod ligands in the co-extraction of lanthanides and actinides.
The secondary amine containing ether bonds provided by the invention has the following structural general formula:
in the formula, R1、R2Straight-chain alkyl of carbon atoms 6-16, which may be the same or different, n is 0 or 1.
Compared with the existing secondary amine, the secondary amine containing ether bonds not only has greater flexibility, but also is simpler and more convenient in the aspect of prolonging the number of atoms.
The above secondary amine containing an ether bond, R1、R2Any of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, straight-chain alkyl groups may be used. Of course, the above is only for R1、R2Examples of (1), R1、R2May not be limited to these groups.
The preparation method of the secondary amine containing the ether bond comprises the steps of firstly converting benzylamine into tertiary benzylamine compounds through aminolysis reaction of alkyl halides, then carrying out substitution reaction of halides and the tertiary benzylamine compounds, and debenzylating the obtained products through chloroformate derivatives to obtain the secondary amine containing the ether bond.
When preparing secondary amines containing ether linkages1、R2When not identical, the method specifically comprisesThe method comprises the following steps:
(1) according to the following synthesis scheme I, potassium carbonate, potassium iodide and alkyl halide with the structural formula (2) are added into a solvent I in which benzylamine is dissolved under the condition of stirring at normal temperature, and then heating reflux reaction is carried out for at least 10 hours. After the reaction is finished, performing suction filtration, performing rotary evaporation to remove the solvent I, and purifying to obtain the tertiary benzylamine compound with the structural formula (3), wherein the volume ratio of the amount of benzylamine to the solvent I is 1 (2500-5000), the amount of substance is mol, the volume unit is mL, and the molar ratio of benzylamine, alkyl halide, potassium carbonate and potassium iodide is 1 (2.5-4) to (2-5) to (0.01-0.02).
In the structural formula (2), X is Cl, Br or I; if X is I, potassium iodide is not required to be added;
(2) according to the following synthesis route II, under the stirring condition, adding an alkali I into a solvent II in which a tertiary benzylamine compound with the structural formula (3) is dissolved, reacting at normal temperature for 1-3 hours, and then adding R1And heating the halide X to reflux for at least 10 h. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation to remove the solvent II, and purifying to obtain the amine compound I with the structural formula (4). Wherein the volume ratio of the substance quantity of the tertiary benzylamine compound with the structural formula (3) to the solvent II is 1 (2500-5000), the substance quantity unit is mol, the volume unit is mL, and the tertiary benzylamine compound with the structural formula (3) and R are1The molar ratio of the X halide to the alkali I is 1 (1-2) to 1-2;
(3) according to the following synthetic route II, under the stirring condition, adding an amine compound I with a structural formula (4) into a solvent II in an ice-water bath at 0-10 ℃ until the amine compound I is completely dissolved, then adding an alkali II at the temperature until the surface of the solution is stable and no bubbles are generated, raising the temperature to normal temperature to continue reacting for 1-3 hours, and then adding R2And (3) halogenating the compound X, and heating and refluxing the compound for reaction for at least 10 h. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation to remove the solvent II, and purifying to obtain the amine compound II with the structural formula (5). Wherein the volume ratio of the substance of the amine compound I with the structural formula (4) to the solvent II is 1 (2500-5000), and the substanceIn mol and in mL, an amine compound I, R of formula (4)2The molar ratio of the X halide to the alkali II is 1 (1-2) to 1-2;
(4) according to the following synthesis route III, under the stirring condition, mixing an amine compound II with a structural formula (5) with a chloroformate derivative, heating and refluxing at 60-120 ℃ for 3-10 h to remove the redundant chloroformate derivative, adding methanol, continuing to heat and reflux at 40-60 ℃ for 3-5 h, removing the redundant methanol, and purifying to obtain a secondary amine with a structural formula (6); wherein the ratio of the amount of the amine compound II with the structural formula (5) to the volume of the chloroformate derivative to the volume of the methanol is 0.05 (100-200) to (100-200), the amount of the substance is mol, and the volume is mL;
process for the preparation of the above ether bond-containing secondary amines for R1、R2The same or different cases may be implemented.
In the above method for producing a secondary amine having an ether bond, the object of the step (1) is to obtain a hydroxyl-protected tertiary amine by reacting benzylamine with a hydroxyl-containing halogenated hydrocarbon, wherein potassium carbonate provides an alkaline environment for the reaction, and thus sodium carbonate, a mixture of sodium carbonate and potassium carbonate may be used instead. Potassium iodide is used as a catalyst. The solvent I is any one of 1, 4-dioxane, acetone, butanone, dichloromethane, tetrahydrofuran, benzene, toluene, etc., and acetone and tetrahydrofuran are preferred. The solvent I can be removed by rotary distillation or reduced pressure distillation, and the purification can be carried out by adopting a column chromatography method.
In the above-mentioned process for producing a secondary amine having an ether bond, the purpose of the steps (2) and (3) is to obtain a compound having-OR group by nucleophilic substitution to ether1、-OR2Tertiary amine compounds of ether bond. The substitution reaction of the halide and the tertiary benzylamine compound is divided into two steps, wherein the substitution reaction in the first step is performedThe basicity of the base I is weaker than that of the base II used in the second substitution, so that the hydrogen of one hydroxyl group on the tertiary benzylamine compound is substituted in the first substitution reaction, and the hydrogen of the other hydroxyl group on the tertiary benzylamine compound is substituted by the base II with stronger basicity in the second substitution reaction. The alkali I is at least one of sodium hydroxide, potassium carbonate, potassium hydroxide, sodium carbonate and the like, wherein the sodium hydroxide is most convenient and has better effect; the alkali II is at least one of sodium hydride, potassium tert-butoxide, sodium ethoxide, sodium amide, sodium isopropoxide, butyl lithium and the like, wherein the sodium hydride is most convenient and has better effect. The solvent II is any one of tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, benzene or toluene, and the like, and tetrahydrofuran is preferred; the solvent II is preferably a solvent after water removal, so that the reaction yield can be improved. R1X halides and R2R in the X halide1、R2Any of octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl straight-chain alkyl groups can be used, X is Br with the best effect, R is1Ratio R2Short chain length of (a) and higher synthesis yield. The solvent II can be removed by rotary evaporation or reduced pressure distillation, and the mixture from which the solvent II is removed is purified by adopting a column chromatography method.
In the above-mentioned method for producing a secondary amine having an ether bond, the object of step (4) is to perform debenzylation reaction of amine compound II of structural formula (5) with a chloroformate derivative. The chloroformate derivative may be any one of ethyl chloroformate, vinyl chloroformate, 1-chloroethyl chloroformate, beta-trichloroethyl chloroformate or beta-trimethylsilyl chloroformate, etc., wherein 1-chloroethyl chloroformate is the most common and easily available. And (3) after the reaction of the amine compound II with the chloroformate derivative is finished, adding methanol into the residue after removing the redundant chloroformate derivative for continuous reaction, removing the redundant methanol by rotary evaporation after the reaction is finished, and finally purifying the mixture after removing the methanol by adopting a column chromatography method or an ether recrystallization method. Taking ethyl chloroformate as an example, the tertiary amine of the amine compound II with the structural formula (5) and ethyl chloroformate are heated to react to obtain carbamate, and the carbamate is heated in methanol to remove the carbamate to obtain the secondary amine with high yield. The final purification method is selected according to the synthesis of different secondary amines, and experiments show that when the number of continuous carbon atoms after alkane substitution is more than or equal to 6, the obtained secondary amine is white flocculent solid and can be purified by adopting a method of recrystallization in diethyl ether. The specific method comprises the following steps: and (3) decompressing the mixed solution obtained by the reflux reaction in the step (4) to remove methanol, adding the obtained product into diethyl ether with the volume ratio of about 1.5-2.5, shaking up, standing at the temperature of below 0 ℃, cooling and separating out, and performing suction filtration, diethyl ether washing and drying to obtain the required secondary amine.
When preparing secondary amines containing ether linkages1、R2Meanwhile, the one-step substitution reaction can be directly carried out in a strong alkaline environment, and based on the method, the steps can be simplified as follows:
(1) according to the following synthesis scheme I, potassium carbonate, potassium iodide and alkyl halide with the structural formula (2) are added into a solvent I in which benzylamine is dissolved under the condition of stirring at normal temperature, and then heating reflux reaction is carried out for at least 10 hours. After the reaction is finished, performing suction filtration, performing rotary evaporation to remove the solvent I, and purifying to obtain the tertiary benzylamine compound with the structural formula (3), wherein the volume ratio of the amount of benzylamine to the solvent I is 1 (2500-5000), the amount of substance is mol, the volume unit is mL, and the molar ratio of benzylamine, alkyl halide, potassium carbonate and potassium iodide is 1 (2.5-4) to (2-5) to (0.01-0.02).
In the structural formula (2), X is Cl, Br or I; if X is I, potassium iodide is not required to be added;
(2) according to the following synthetic route IV, under the stirring condition, adding a tertiary benzylamine compound with the structural formula (3) into a solvent II in an ice-water bath at 0-10 ℃ until the tertiary benzylamine compound is completely dissolved, then adding an alkali II at the temperature, after the surface of the solution is stable and no bubbles exist, heating the obtained reaction system to the normal temperature, continuing to react for 1-3 hours, adding R1X halogenated compound, heating and refluxing for reaction for at least 10h, removing solvent, and purifying to obtainTo an amine compound III with a structural formula of (5)', wherein the volume ratio of the substance amount of the tertiary benzylamine compound with the structural formula of (3) to the solvent II is 1 (2500-5000), the substance amount unit is mol, the volume unit is mL, the tertiary benzylamine compound with the structural formula of (3), R1The molar ratio of the X halide to the alkali II is 1 (2-5) to (2-5);
(3) according to the following synthesis route V, under the stirring condition, mixing an amine compound III with a structural formula (5) ' with a chloroformate derivative, heating and refluxing at 60-120 ℃ for 3-10 h to remove the redundant chloroformate derivative, adding methanol, continuing to heat and reflux at 40-60 ℃ for 3-5 h to remove the redundant methanol, and purifying to obtain a secondary amine with a structural formula (6) ' with the mass of the amine compound III with the structural formula (5) ' and the volume of the chloroformate derivative in a methanol volume ratio of 0.05 (100-200): 100-200, wherein the mass unit is mol and the volume unit is mL;
the above-mentioned steps (1) - (3) are explained similarly to the above, and are not described herein again.
In addition, regardless of the above-mentioned preparation method of the secondary amine containing an ether bond, in the case of the tertiary benzylamine compound of the structural formula (3) to be prepared in the step (1), when n is 0, the preparation method of the tertiary benzylamine compound may be:
according to the following synthetic route VI, under the stirring condition, adding potassium carbonate and halogenated benzyl into a solvent I in which diethanol amine is dissolved, heating and refluxing for 8-10 h, cooling the obtained reaction liquid to normal temperature, performing suction filtration on the obtained filtrate, removing the solvent I, and purifying to obtain a tertiary benzylamine compound with the structural formula (3)'; the volume ratio of the mass of the diethanol amine to the solvent I is 1 (2500-5000), the mass unit of the diethanol amine is mol, the volume unit of the diethanol amine is mL, and the molar ratio of the diethanol amine to the halobenzyl to the potassium carbonate is 1 (1-1.2) to 2-3.
The filtrate obtained in the preparation method of the tertiary benzylamine compound is subjected to spin drying or reduced pressure distillation to remove the solvent I, and then is purified by a method of passing ethyl acetate through a column to obtain the tertiary benzylamine compound with the structural formula (3)'. Compared with the preparation method provided by the prior art, the method for preparing the tertiary benzylamine compound has the advantages of easily available and cheap raw materials and less reaction impurities.
The invention further provides an amide podophyllum ether ligand, which has the following structural general formula:
in the formula, R1、R2Straight-chain alkyl, branched-chain alkyl or cyclic alkyl of carbon atoms 8-16, which may be the same or different, n is 0 or 1.
The amide podophyllum ether ligand contains secondary amine containing ether bond, so that the amide podophyllum ether ligand has very good solubility in alkane compound solution. When the amide podophyllum ether ligand is used as an extractant of a lanthanide and actinide co-extraction system, the formation of three phases can be effectively inhibited under higher metal ion concentration or nitric acid concentration. In addition, the amide podophyllum ether ligand only contains C, H, O, N four elements at the same time, and the amide podophyllum ether ligand is used as an extracting agent of a lanthanide and actinide co-extraction system, so that the radiation resistance stability of the separation extraction system can be greatly improved, secondary pollutants cannot be generated, and the environment protection is facilitated.
The invention further provides a method for preparing an amide podand ether ligand by using the secondary amine containing ether bonds as a raw material, which is carried out by two steps according to the following synthetic route: (1) reacting diglycolic acid with thionyl chloride to generate diglycolic chloride; (2) reacting diglycoyl chloride with a secondary amine containing an ether linkage prepared by any of the above methods to form an amide podophyllum ether ligand.
The method specifically comprises the following steps:
(1) heating and refluxing diglycolic acid and thionyl chloride at 40-60 ℃ for 6-8 h, distilling under reduced pressure by using a water pump, and collecting fractions at 110-130 ℃ under the vacuum degree of 0.1-0.15 MPa to obtain pale yellow oily diglycolic chloride, wherein the volume of the diglycolic acid is 0.05 (100-200) of the volume of the thionyl chloride, the amount unit of the diglycolic acid is mol, and the volume unit is mL;
(2) under the condition of stirring, adding secondary amine containing ether bond and acid-binding agent into solvent IV<Mixing and stirring in a 5 ℃ ice salt bath, dropwise adding diglycolic chloride in the stirring process, continuing to react for 1-2 h after dropwise adding is finished, then heating to room temperature, reacting for at least 3h, performing suction filtration, washing obtained filtrate to be neutral by acid liquor, alkali liquor and water in sequence, and washing an organic layer by anhydrous Na2SO4And drying, filtering, removing a solvent IV and purifying to obtain the amide podophyllum ether ligand, wherein the molar ratio of the diglycolic chloride, the secondary amine containing ether bonds and the acid-binding agent is 1 (2-3) to 0.4-1, and the solvent IV is benzene or dichloromethane.
The thionyl chloride is used as both a reactant and a solvent in the above preparation method of the amide podand ligand.
The acid-binding agent used in the preparation method of the amide podophyllum ether ligand is pyridine or triethylamine; the acid solution used for washing is hydrochloric acid solution or nitric acid solution; the alkali liquor is sodium hydroxide solution, saturated sodium carbonate solution or saturated sodium bicarbonate solution; removing the solvent IV by adopting a distillation method, and purifying the crude product from which the solvent IV is removed by adopting a column chromatography method.
The invention further provides application of the amide podophyllum ether ligand prepared by the method in separation and extraction of lanthanide and actinide, which is used for preparing a lanthanide and actinide co-extraction system, wherein the extraction system is formed by equal-volume mixing of an organic phase and an aqueous phase, the organic phase contains the amide podophyllum ether ligand with a molar concentration of 0.1-0.7 mol/L as an extracting agent, and the amide podophyllum ether ligand is preferably selected from TOOEDGA (see example 8), TNOEDGA (see example 9), TDOEDGGA (see example 10) and TDdOEDGA (see example 11), and the extracting agent is preferably selected from 0.1-0.6 mol/L; the aqueous phase of choice contains the lanthanides and actinides to be extracted.
The organic phase in the lanthanide and actinide co-extraction system is a long-chain alkane compound solution of amide pod ether ligand, wherein the long-chain alkane compound is used as a diluent, and the long-chain alkane compound is not strictly required, so long as the non-polar alkane compound can be used as the diluent, and generally any one of n-alkanes with 6-12 carbon atoms, such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane or n-dodecane, etc. Therefore, compared with the traditional lanthanide series and actinide series extraction system, the application range of the separation extraction system can be expanded.
The aqueous phase in the lanthanide and actinide co-extraction system is a nitric acid aqueous solution of lanthanide and actinide ions to be extracted, wherein the molar concentration of the nitric acid is 1.0-4.0 mol/L.
Stirring the organic phase and the water phase in the lanthanide and actinide co-extraction system at room temperature for 0.25-2 h, preferably 0.5-1 h; and after stirring, separating the organic phase from the water phase by adopting a conventional centrifugal means, thereby realizing the co-extraction of the lanthanide and the actinide.
Lanthanides that can be used in the above-described lanthanide and actinide co-extraction system to achieve co-extraction include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, and actinides include thorium, uranium, americium, and curium.
Compared with the prior art, the invention has the following beneficial effects:
1. the secondary amine prepared by the invention contains ether bonds, has higher flexibility than the simple carbon chain secondary amine, and is easy to extend the number of carbon atoms, so that the secondary amine candidate with excellent performance is provided for the fields of organic synthetic chemistry and pharmaceutical chemistry.
2. The preparation method of the secondary amine provided by the invention is characterized in that benzylamine is used as a raw material, and the secondary amine containing ether bonds is prepared through aminolysis, substitution reaction and debenzylation, so that the preparation method is simple to operate, mild in reaction conditions and easy to obtain raw materials, the manufacturing difficulty and production cost of the secondary amine are greatly reduced, and the yield and purity of the secondary amine are greatly improved due to the absence of side reactions.
3. Because the amide podand ligand prepared by the invention contains secondary amine containing ether bond, the amide podand ligand has very good solubility in alkane compound solution, so that alkane compound which is commonly used in industry can be used as diluent in spent fuel aftertreatment.
4. Because the ether oxygen chain exists in the secondary amine containing the ether bond of the amide podand ether ligand prepared by the invention, the ether oxygen chain is used as an extractant of a lanthanide and actinide co-extraction system in spent fuel aftertreatment, and the formation of three phases can be effectively inhibited under higher metal ion concentration or nitric acid concentration.
5. Because the amide pod ether ligand prepared by the invention has a unique long-chain alkoxy ether chain and only contains C, H, O, N four elements, the amide pod ether ligand is used as an extracting agent of a lanthanide and actinide co-extraction system, so that the radiation-resistant stability of the separation and extraction system can be greatly improved, secondary pollutants cannot be generated, and the environment protection is facilitated.
6. The lanthanide and actinide separation and extraction system using the amide podand ether ligand as the extractant provided by the invention can realize a good separation effect in an acidity range of industrial application, so that the system has strong practicability and also has a good application prospect in the field of advanced nuclear fuel circulation.
Drawings
FIG. 1 is an IR spectrum of bis (2-ethoxyoctyl) amine prepared in example 1 of the present invention.
FIG. 2 shows bis (2-ethoxyoctyl) amine prepared in example 1 of the present invention1H NMR spectrum.
FIG. 3 is a mass spectrum of bis (2-ethoxyoctyl) amine prepared in example 1 of the present invention.
FIG. 4 is an IR spectrum of TOOEDGA prepared in example 7 of the present invention.
FIG. 5 shows TOOEDGA prepared in example 7 of the present invention1H NMR spectrum.
FIG. 6 is a TOOEDGA mass spectrum prepared in example 7 of the present invention.
Fig. 7 is a three-phase analysis picture of an extraction system of application example 45 and application comparative example 12 of the present invention.
Fig. 8 is a three-phase analysis picture of an extraction system of application example 46 and application comparative example 13 of the present invention.
Fig. 9 is a three-phase analysis picture of an extraction system of application example 47 and application comparative example 14 of the present invention.
FIG. 10 is a three-phase analysis picture of the extraction system of application examples 48-51 and application comparative example 15 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.