Preparation method and application of water-soluble transient supramolecular organic framework material

Abstract

A preparation method and application of a water-soluble transient supramolecular organic framework material belongs to the technical field related to supramolecular organic framework materials. The present invention designs a methyl viologen derivative molecule as one of the assembly units, which is converted into a methyl viologen free radical and cucurbituril self-assembled under the action of a reducing agent to form a supramolecular organic framework material in water. The formation of the assembly is regulated by the reducing agent. When the reducing agent is completely consumed, the supramolecular organic framework spontaneously disassembles, showing time controllability. The transient supramolecular organic framework designed by the present invention can be used as a nanoreactor in the aqueous phase to achieve efficient and green synthesis of catalytic organic matter in water and spontaneous release of the product.

Description

Technical Field

[0001] The present invention belongs to the technical field related to supramolecular organic framework materials, and specifically relates to a preparation method and application of a water-soluble transient supramolecular organic framework material. Background Art

[0002] Traditional synthesis methods widely use organic solvents, which not only bring environmental pollution problems, but also have problems such as high production costs and low operational safety. Currently, the reaction of synthesizing benzyl sulfone compounds using methyl viologen as catalyst usually needs to be carried out in highly polar organic solvents (such as DMF and DMSO). However, these highly polar organic solvents are toxic and difficult to remove, and there is a problem that methyl viologen residues are difficult to completely remove, thereby increasing the cost and complexity of purifying the target product and affecting the purity of the product.

[0003] To address these issues, the concept of green chemistry advocates the use of environmentally friendly synthesis methods. Water, as a non-toxic, non-polluting, and inexpensive solvent, is gaining increasing attention. In particular, water's polarity and hydrogen-bonding properties give it unique advantages in chemical reactions.

[0004] However, for hydrophobic compounds, due to their low solubility in water, it is usually necessary to add a surfactant to increase the solubility of the hydrophobic compound in water, improve the reaction environment, and thus increase its reactivity. Even the surfactant itself can act as a catalyst or co-catalyst, participate in the reaction process, and further improve the reaction rate and efficiency. However, after using a surfactant in the aqueous phase synthesis compound process, the surfactant must be effectively removed to ensure the purity and safety of the final product. Common methods include extraction, dialysis, adsorption, precipitation, and ultrafiltration. Although there are various methods that can be used to remove surfactants, it is still difficult to thoroughly remove them. Especially in drug synthesis, residual surfactants may affect the purity and biocompatibility of the product. In addition, the complicated purification steps increase energy consumption and cost.

[0005] Therefore, developing a green synthesis method for synthesizing hydrophobic organic compounds in aqueous phase to solve the problems of environmental pollution, high production cost, low operational safety, complex purification process caused by the extensive use of organic solvents in traditional hydrophobic organic compound synthesis methods, and the difficulty in completely removing surfactants in existing aqueous phase organic synthesis methods will have great economic and social benefits.

[0006] Supramolecular organic frameworks (SOFs) are an emerging class of porous, two-dimensional frameworks formed by connecting small organic monomers through non-covalent interactions. They have broad applications in fields such as gas adsorption and catalysis. Currently, there are no reports on methods for constructing transient self-assembling SFOs or their application in aqueous green synthesis. Summary of the Invention

[0007] In response to the above-mentioned problems existing in the prior art, the purpose of the present invention is to design and provide a technical solution for the preparation method and use of water-soluble transient supramolecular organic framework materials. The invention realizes a transient self-assembled material that spontaneously disassembles and releases the target product after catalytic synthesis of compounds in the aqueous phase, and uses it in the field of aqueous phase organic synthesis. The purification and post-processing operation steps are simple, and the synthesis of the target product is efficient and environmentally friendly.

[0008] The present invention provides a method for preparing a water-soluble transient supramolecular organic framework material, comprising:

[0009] The reducing agent drives the two assembly substrate molecules of methyl viologen derivative and cucurbit[8]uril (i.e., the assembly substrate is completely dissolved in the solvent) to self-assemble in the solvent to form a supramolecular organic framework material; after the reducing agent reacts completely, the supramolecular organic framework material automatically disassembles into the two assembly substrate molecules in the solvent; the self-assembly and automatic disassembly processes cooperate to constitute the transient characteristics of the supramolecular organic framework material, i.e., the assembly state, disassembly state and solvent system of the supramolecular organic framework material together constitute the transient supramolecular organic framework material; the conversion between the assembly state and disassembly state of the supramolecular organic framework material in the transient supramolecular organic framework material is reversibly regulated by the amount of reducing agent used; the solvent is water, preferably selected from one of ultrapure water, deionized water, pure water or distilled water.

[0010] The reducing agent can drive the self-assembly of methyl viologen derivatives and cucurbit[8]uril, and after the reducing agent is completely consumed, the supramolecular organic framework material formed by the self-assembly spontaneously disassembles. The fundamental reason is that the existence of the reducing agent can ensure the survival of the methyl viologen derivative free radicals.

[0011] The conversion between the assembled state and the disassembled state of the transient supramolecular organic framework material in the transient supramolecular organic framework material is reversibly regulated by the amount of reducing agent used, which determines that the transient supramolecular organic framework material has potential value for recycling in practical applications.

[0012] Preferably, the chemical structural formula of the methyl viologen derivative is selected from one of the following structures:

[0013]

[0014] This is because the planar structure of the above preferred small molecule monomers of methyl viologen derivatives is more easily self-assembled to form supramolecular organic framework materials.

[0015] Preferably, the molar ratio of the cucurbit[8]uril, methyl viologen derivative and reducing agent is 1:(1-10):(4-1000).

[0016] The reducing agent is a water-soluble reducing agent, preferably selected from one or more of sodium dithionite, hydrazine hydrate, sodium ascorbate, and sodium borohydride.

[0017] In order to more intuitively present the specific experimental steps of the preparation method of the water-soluble transient supramolecular organic framework material, the solvent water is ultrapure water as an example, and the dissolution method is ultrasonic dissolution as an example for explanation. This should not be understood as limiting the present invention. The specific experimental steps are as follows:

[0018] 1) Under room temperature, first dissolve the methyl viologen derivative in ultrapure water by ultrasonication, then add cucurbituril and ultrasonicate again until the cucurbituril is completely dissolved;

[0019] 2) after adding the reducing agent, the methyl viologen derivative and cucurbit[8]uril self-assemble to form a supramolecular organic framework;

[0020] 3) When the reducing agent is completely consumed, the reducing agent in step 2) reduces the methyl viologen derivative molecules to obtain methyl viologen free radicals, which are oxidized by oxygen in the air, resulting in spontaneous disassembly of the supramolecular organic framework.

[0021] The present invention also provides a water-soluble transient supramolecular organic framework material prepared by the method for preparing the water-soluble transient supramolecular organic framework material.

[0022] The water-soluble transient supramolecular organic framework material provided by the present invention is a supramolecular organic framework based on a methyl viologen base, namely: a methyl viologen derivative small molecule monomer, which forms a methyl viologen derivative small molecule monomer free radical under the reduction action of a reducing agent, and then self-assembles to form a porous framework material with a two-dimensional structure through non-covalent interaction, while cucurbit[8]uril plays a similar "snap" function, to some extent, stabilizing the non-covalent interaction between the methyl viologen derivative small molecule monomers. When the reducing agent is completely consumed, the methyl viologen derivative small molecule monomer free radical is quenched and inactivated, so that the non-covalent interaction force is greatly weakened, which is insufficient to maintain the stability of the supramolecular organic framework material, and the supramolecular organic framework material automatically disassembles.

[0023] The assembly structure of the transient supramolecular organic framework material provided by the present invention changes with the structure of the small molecule monomer of the methyl viologen derivative. As a preference, it involves three different methyl viologen-based supramolecular organic frameworks, specifically including: tetramethyl viologen tetraphenylethylene SOF (SOF-1), assembly structure formula Trimethyl viologen triphenylbenzene SOF (SOF-2), assembled structure Tetramethyl viologen tetraphenylporphyrin SOF (SOF-3), assembled structure

[0024] Among them, SOF-1 is formed by reducing the monomer molecule tetramethyl viologen tetraphenylethylene with a reducing agent to self-assemble into tetramethyl viologen free radical tetraphenylethylene and cucurbit[8]uril, SOF-2 is formed by reducing the monomer molecule trimethyl viologen triphenylbenzene with a reducing agent to self-assemble into trimethyl viologen free radical triphenylbenzene and cucurbit[8]uril, and SOF-3 is formed by reducing the monomer molecule tetramethyl viologen tetraphenylporphyrin with a reducing agent to self-assemble into tetramethyl viologen free radical tetraphenylporphyrin and cucurbit[8]uril.

[0025] The schematic diagram of the self-assembly reaction principle of SOF-1 is shown below:

[0026]

[0027] For the purpose of illustrative purposes, the reducing agent selected in the SOF-1 principle diagram is sodium dithionite (SDT) and the free radical deactivator is oxygen (O2), which should not be construed as limiting the present invention.

[0028] In addition, the schematic structure of cucurbit[8]uril in the schematic diagram of the self-assembly reaction principle of SOF-1 This is commonly used in this article when displaying assembly structures, so please note this.

[0029] The present invention also provides an application of the water-soluble transient supramolecular organic framework material in the field of organic synthesis technology, especially a green and environmentally friendly application in the field of aqueous organic synthesis.

[0030] Traditional organic synthesis processes widely use organic solvents as solvents, which have a series of problems such as high warehouse management risks, high production process safety management costs, low production operation safety, and three waste environmental pollution emissions. In order to solve these problems of traditional organic synthesis processes, the concept of green chemistry advocates the use of environmentally friendly synthesis methods. The solvent for aqueous organic synthesis is water, which has the advantages of being non-toxic, pollution-free and cheap, and is increasingly valued. However, for hydrophobic compounds, due to their low solubility in water, surfactants are usually required to increase the solubility of hydrophobic compounds in water and improve the reaction rate and efficiency. However, the post-processing removal of traditional surfactants is very difficult, which ultimately affects the practical application of the target product.

[0031] The water-soluble transient supramolecular organic framework material provided by the present invention is essentially a special type of surfactant, which is used in aqueous organic synthesis and has the following two unique advantages: 1) The hydrophobic backbone portion of the organic framework material itself of the water-soluble transient supramolecular organic framework material can increase the solubility of hydrophobic compounds in water, playing a role similar to a nanoreactor / nanoreaction platform, thereby improving the reaction rate and efficiency of aqueous organic synthesis; 2) The water-soluble transient supramolecular organic framework material also has the characteristic of spontaneous disassembly and can spontaneously disassemble and release the reaction product after the synthesis of the reaction product is completed. In other words, the transient characteristics of the water-soluble transient supramolecular organic framework material specifically solve the pain point problem of difficult post-processing removal of traditional surfactants.

[0032] In addition, the water-soluble transient supramolecular organic framework material described in the present invention is a supramolecular organic framework based on methyl viologen. During its assembly and formation process, the methyl viologen derivative small molecule monomer will form methyl viologen derivative small molecule monomer free radicals under the reduction action of a reducing agent, and the methyl viologen derivative small molecule monomer free radicals can just serve as a catalyst for the sulfonation reaction. Preferably, the water-soluble transient supramolecular organic framework material described in the present invention is further used in the sulfonation reaction of aqueous organic synthesis.

[0033] Currently, the synthesis of benzyl sulfone compounds in sulfonation reactions typically requires the use of methyl viologen as a catalyst in highly polar organic solvents (such as DMF and DMSO). However, these highly polar organic solvents generally have high boiling points, are toxic, and are difficult to remove. Furthermore, residual methyl viologen is difficult to completely remove, increasing the cost and complexity of purifying the target product, affecting its purity and, consequently, hindering its application and promotion.

[0034] The present invention also provides a green and environmentally friendly method for synthesizing a benzyl sulfone compound in an aqueous phase, comprising:

[0035] Aromatic benzyl bromide and potassium phosphate are added to an aqueous solution containing a methyl viologen derivative and cucurbit[8]uril. After an inert gas is introduced to remove oxygen, the reducing agent sodium dithionite is added to drive the formation of a transient supramolecular organic framework (SOF) and catalyze the formation of benzyl sulfone. After the reaction is completed, exposure to oxygen in the air causes the transient SOF to disassemble and release the benzyl sulfone product, which can be obtained in pure form by simple filtration or extraction.

[0036] Preferably, the above reaction is carried out in a sealed container under the protection of an inert gas, and the inert gas can be any inert gas commonly used in the art, such as nitrogen, argon, etc.

[0037] Experiments have shown that the aqueous phase synthesis method for benzyl sulfone compounds provided by the present invention is simple to operate, has convenient post-processing and purification steps, and has a target product yield of over 80%. It eliminates the problem of discharging and treating a large amount of organic solvent waste liquid generated by the traditional organic phase synthesis of benzyl sulfone compounds, and is highly efficient and environmentally friendly.

[0038] Compared with the prior art, the present invention has the following beneficial technical effects:

[0039] 1) The transient water-soluble supramolecular organic framework material provided by the present invention can be formed in situ by spontaneous self-assembly of the assembly substrate molecules in the aqueous solution of the assembly substrate by driving the assembly substrate molecules with a reducing agent. It is used in the field of aqueous organic synthesis of hydrophobic compounds, can increase the solubility of hydrophobic reaction substrates, and efficiently catalyze the green synthesis of reaction products.

[0040] 2) The transient water-soluble supramolecular organic framework material provided by the present invention is sensitive to oxygen in the air. In the actual process operation of aqueous organic synthesis, after the reactants complete the reaction in the aqueous phase, the transient water-soluble supramolecular organic framework material can be spontaneously disassembled and released by exposing the reaction system to air. This greatly simplifies the purification and post-treatment process of traditional aqueous organic synthesis, solves the problem of difficult removal of surfactant residues in traditional aqueous organic synthesis processes, eliminates multiple purification process flows, and has potential application value in production cost control and capacity improvement.

[0041] 3) The transient water-soluble supramolecular organic framework material provided by the present invention is a transient assembly structure driven by a reducing agent. After the reducing agent is exhausted and the supramolecular framework material disassembles, the reducing agent can be added again to re-drive the self-assembly-disassembly cycle of the supramolecular organic framework material, thereby realizing multiple recycling of the transient water-soluble supramolecular organic framework material and saving costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is the H NMR spectrum of the intermediate A involved in Example 1;

[0043] Figure 2 This is the H NMR spectrum of the tetramethyl viologen tetraphenylethylene monomer molecule involved in Example 1;

[0044] Figure 3 This is an ultraviolet spectrum diagram of the dynamic change process of SOF-1 material in Example 1;

[0045] Figure 4 Schematic diagram of the reaction principle for preparing the transient supramolecular organic framework material SOF-1 in Example 1;

[0046] Figure 5 TEM image of transient SOF-1 material assembly in Example 1;

[0047] Figure 6 This is a kinetic diagram of the recycling of transient SOF-1 materials in Example 1;

[0048] Figure 7 Application Example 1 involves the H NMR spectrum of benzyl sulfone 2a, a product synthesized by transient SOF-1 material;

[0049] Figure 8 Application Example 1 involves the aqueous green synthesis of transient SOF-1 materials and a schematic diagram of the transient assembly of spontaneously released benzyl sulfone. DETAILED DESCRIPTION

[0050] The specific implementation method of the present invention is further described below in conjunction with the drawings and examples of the specification. It should be noted here that the specific implementation method described here is only for illustrating and explaining the present invention and is not intended to limit the scope of protection of the present invention.

[0051] Example 1

[0052] This embodiment provides a method for preparing a transient supramolecular organic framework material based on tetramethyl viologen tetraphenylethylene, comprising the following steps:

[0053] 1) Synthesis of tetramethyl viologen tetraphenylethylene monomer molecules:

[0054] (a) Synthesis of Intermediate A

[0055] Tetrakis-(4-aminophenyl)ethylene and 1-(2,4-dinitrophenyl)-4-phenylpyridinium chloride were dissolved in ethanol at a molar ratio of 1:16, and the mixture was refluxed for 3 days. After removing the ethanol, acetonitrile was added for washing and the solid was collected by filtration. The solid was dissolved in a small amount of water, 10% ammonium hexafluorophosphate was added, the precipitated solid was collected and vacuum dried, and the yellow solid was dissolved in acetonitrile, 10% tetrabutylammonium chloride was added, and the precipitated solid was collected by filtration. After vacuum drying, an orange solid (Intermediate A) was obtained with a yield of 86%. The H NMR spectrum of the intermediate A is shown as follows: Figure 1 shown.

[0056] (b) Synthesis of Tetramethyl Viologen Tetraphenylethylene Monomer

[0057] The intermediate obtained in step (a) was dissolved in DMF with methyl iodide at a molar ratio of 1:10, and the mixture was reacted at 75° C. for 48 hours. The solvent was removed by rotary evaporation, and the red solid obtained after washing with acetonitrile, filtering, collecting, and drying was tetramethyl viologen tetraphenylethylene monomer with a yield of 88%. The H NMR spectrum of the tetramethyl viologen tetraphenylethylene monomer was as follows: Figure 2 shown.

[0058] The structural formula of the tetramethyl viologen tetraphenylethylene monomer molecule is:

[0059]

[0060] 2) Preparation of transient supramolecular organic framework materials based on tetramethyl viologen tetraphenylethylene:

[0061] Tetramethyl viologen tetraphenylethylene monomer molecules and cucurbit[8]uril were added to a sample bottle in a molar ratio of 1:2, and 1 mL of ultrapure water was added to make the total mass concentration of tetramethyl viologen tetraphenylethylene monomer molecules and cucurbit[8]uril in the solution reach 8.7 g / L. Ultrasonic oscillation was performed for 20 minutes to completely dissolve them, and then 7 mg of sodium dithionite was added. The sample bottle was shaken to mix well and then allowed to stand. In situ dynamics of the transient supramolecular organic framework material SOF-1 (hereinafter referred to as transient SOF-1) was detected by ultraviolet spectroscopy. The results are as follows: Figure 3 As shown, the absorption intensity at 650 nm, corresponding to the methyl viologen radical, shows a temporal trend of first increasing and then decreasing, confirming the presence of transient methyl viologen radicals. The absorption intensity at 1000 nm corresponds to the assembly of methyl viologen radicals, and its variation trend is similar to that at 650 nm, confirming the presence of transient assemblies. UV spectroscopy demonstrates the kinetics of supramolecular assembly and disassembly.

[0062] UV spectroscopy was used to detect the in situ dynamics of transient SOF-1. Simultaneously, the time monitoring experiment showed that in the solution after sodium dithionite was added and mixed evenly in step 2), the assembly substrates (tetramethyl viologen tetraphenylethylene monomer molecules and cucurbit[8]uril) began to self-assemble to form a two-dimensional supramolecular organic framework material, reaching the maximum assembly degree at 1 minute. Subsequently, as the reducing agent was consumed, the assembly gradually disassembled and completely returned to the solution state at 28 minutes. Thus, a reaction assembly cycle of the transient supramolecular organic framework material SOF-1 was successfully realized. The reaction principle diagram of the transient supramolecular organic framework material SOF-1 is shown in the figure. Figure 4 As shown in the figure. This experimental phenomenon shows that: tetramethyl viologen tetraphenylethylene monomer molecules, as one of the assembly units, self-assemble with cucurbit[8]uril under the action of a certain amount of reducing agent sodium dithionite, and can quickly (1 minute) form a supramolecular organic framework material assembly in water. When the sodium dithionite is completely consumed, the supramolecular organic framework spontaneously disassembles and completely returns to the solution state in 28 minutes, showing time controllability.

[0063] The transient assembly morphology of the transient SOF-1 in this embodiment was characterized by TEM test. The TEM test results are shown in FIG. Figure 5 As shown: The transient self-assembled structure formed a two-dimensional lamellar structure with a diameter of tens of microns, confirming that the transient assembly formed was a supramolecular organic framework material.

[0064] In addition, an experiment was conducted to explore the number of times the transient SOF-1 can be reused. For the transient supramolecular organic framework material driven by the reducing agent in this embodiment, after the reducing agent is completely consumed and the supramolecular framework material disassembles, the reducing agent can be added again to drive the formation of the transient supramolecular framework material again. The changes in the absorption intensity of the solution at 600nm were monitored by ultraviolet spectroscopy, as shown in FIG. Figure 6 The kinetic diagram of the recycling of transient SOF-1 materials shown confirms that the transient supramolecular framework material can be repeated at least 10 times by multiple additions of reducing agents.

[0065] Example 2

[0066] This embodiment provides a method for preparing a transient supramolecular organic framework material based on trimethyl viologen triphenylbenzene:

[0067] Trimethyl viologen triphenylbenzene monomer molecules and cucurbit[8]uril were added to a sample bottle at a molar ratio of 1:1, and 1 mL of ultrapure water was added. At this time, the total mass concentration of trimethyl viologen triphenylbenzene monomer molecules and cucurbit[8]uril in the solution was 6.5 g / L. After ultrasonic oscillation for 20 minutes to completely dissolve, 560 mg of sodium ascorbate was added and the sample bottle was shaken to mix evenly and then allowed to stand. At this time, the solution began to self-assemble to form a two-dimensional supramolecular organic framework material, reaching the maximum assembly degree at 5 minutes. Subsequently, as the reducing agent was consumed, the assembly gradually disassembled and completely returned to the solution state at 12 hours, thus successfully preparing a transient SOF-2 system.

[0068] Among them, the structural formula of trimethyl viologen triphenylbenzene monomer molecule is:

[0069]

[0070] In this embodiment, trimethyl viologen triphenylbenzene monomer molecules were prepared according to the preparation method reported in the literature (Polymer. Chemistry., 2014, 5, 4715-4721).

[0071] Example 3

[0072] This embodiment provides a method for preparing a transient supramolecular organic framework material based on tetramethyl viologen tetraphenylporphyrin:

[0073] Tetramethyl viologen tetraphenylporphyrin monomer molecules and cucurbit[8]uril were added to the sample bottle at a molar ratio of 1:10, and 1 mL of ultrapure water was added. At this time, the total mass concentration of trimethyl viologen triphenylbenzene monomer molecules and cucurbit[8]uril in the solution was 10.8 g / L. After ultrasonic oscillation for 20 minutes to completely dissolve, 200 mg of hydrazine hydrate was added and the sample bottle was shaken to mix evenly and then allowed to stand. At this time, the solution began to self-assemble to form a two-dimensional supramolecular organic framework material, reaching the maximum assembly degree at 1 minute. Subsequently, as the reducing agent was consumed, the assembly gradually disassembled and completely returned to the solution state at 28 minutes, thus successfully preparing a transient SOF-3 system.

[0074] Among them, the structural formula of tetramethyl viologen tetraphenylporphyrin monomer molecule is:

[0075]

[0076] In this embodiment, tetramethyl viologen tetraphenylporphyrin monomer molecules were prepared according to the preparation method reported in the literature (Polymer. Chemistry., 2015, 6, 1923-1927).

[0077] Application Example 1

[0078] The transient SOF-1 aqueous phase catalyzed synthesis of benzyl sulfone compounds, the reaction scheme is shown below:

[0079]

[0080] A certain amount of tetramethyl viologen tetraphenylethylene monomer, cucurbit[8]uril, benzyl bromide derivative (benzyl bromide) and potassium phosphate were weighed separately in a sealed sample bottle containing a stirrer. The molar ratio of tetramethyl viologen tetraphenylethylene monomer: cucurbit[8]uril: benzyl bromide derivative (benzyl bromide): potassium phosphate was 1:2:50:50. Then 2 mL of ultrapure water was added for ultrasonic dissolution. After completely removing the air by bubbling nitrogen for 15 minutes, 7 mg of sodium dithionite was added, and then magnetic stirring was carried out at room temperature for 16 hours to allow the reaction to be completely converted. The sample bottle was then opened to expose to air and shaken for 1 minute to allow the supramolecular organic framework to spontaneously disassemble and release the benzyl sulfone product (the solution changed from black to transparent). Finally, it was extracted with dichloromethane three times, and the corresponding benzyl sulfone product was obtained after removing the dichloromethane by rotary evaporation. The benzyl sulfone product was characterized by in situ nuclear magnetic hydrogen spectrum, among which the nuclear magnetic properties of the product benzyl sulfone 2a were as follows Figure 7 As shown, the yields of the corresponding benzyl sulfone compounds synthesized by catalysis are as indicated in the reaction scheme diagram, namely: the yield of compound 2a is 100%, the yield of compound 2b is 94%, the yield of compound 2c is 100%, and the yield of compound 2d is 82%.

[0081] There are four kinds of benzyl bromide derivatives described in this application example, including benzyl bromide, 4-methylbenzyl bromide, p-bromobenzyl bromide, and m-chlorobenzyl bromide, which are specially explained here.

[0082] The schematic diagram of the principle of the green synthesis of transient supramolecular organic framework materials in aqueous phase and spontaneous release of benzyl sulfone in this application example is shown in the figure. Figure 8 shown.

[0083] The beneficial effects of the present invention can also be achieved by catalytically synthesizing benzyl sulfone compounds in a transient SOF-2 or SOF-3 aqueous phase.

[0084] The above description is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. The above description of the present invention using specific examples is only used to help understand the present invention and is not intended to limit the present invention. Those skilled in the art of the present invention can also make several simple deductions, modifications, substitutions or combinations based on the concept of the present invention. These deductions, modifications, substitutions or combinations also fall within the scope of the claims of the present invention.

Claims

1. A method for preparing a water-soluble transient supramolecular organic framework material, characterized in that The following steps are involved: The reducing agent drives the two assembly substrate molecules, methyl viologen derivatives and cucurbit[8]uril, to self-assemble in the solvent to form a supramolecular organic framework material; after the reducing agent reaction is complete, the supramolecular organic framework material automatically disassembles into two assembly substrate molecules in the solvent; the self-assembly and automatic disassembly processes cooperate to constitute the transient characteristics of the supramolecular organic framework material, that is, the assembly state, disassembly state and solvent system of the supramolecular organic framework material together constitute the transient supramolecular organic framework material; The conversion between the assembled state and the disassembled state of the supramolecular organic framework material in the transient supramolecular organic framework material is reversibly regulated by the amount of reducing agent used; The reducing agent is a water-soluble reducing agent; The solvent is water; The chemical structural formula of the methyl viologen derivative is: 、 or ; The molar ratio of cucurbit[8]uril:methyl viologen derivative:reducing agent is 1:1-10:4-1000.

2. The method for preparing a water-soluble transient supramolecular organic framework material according to claim 1, wherein: The molar ratio of cucurbit[8]uril:methyl viologen derivative:reducing agent is 1:2-8:10-800.

3. The method for preparing a water-soluble transient supramolecular organic framework material according to claim 1, wherein: The molar ratio of cucurbit[8]uril:methyl viologen derivative:reducing agent is 1:4-6:50-200.

4. The method for preparing a water-soluble transient supramolecular organic framework material according to claim 1, wherein: The water-soluble reducing agent is at least one of sodium dithionite, hydrazine hydrate, sodium ascorbate, and sodium borohydride.

5. The method for preparing a water-soluble transient supramolecular organic framework material according to claim 1, wherein: The solvent water is ultrapure water, deionized water, pure water or distilled water.

6. The method for preparing a water-soluble transient supramolecular organic framework material according to claim 1, wherein: The assembly structure of the transient supramolecular organic framework material changes with the structure of the small molecule monomer of the methyl viologen derivative, specifically including: tetramethyl viologen tetraphenylethylene SOF-1, the assembly structure of , trimethyl viologen triphenylbenzene SOF-2, assembled structure , Tetramethyl viologen tetraphenylporphyrin SOF-3, assembled structure ; Among them, SOF-1 is formed by reducing the monomer molecule tetramethyl viologen tetraphenylethylene with a reducing agent to self-assemble into tetramethyl viologen free radical tetraphenylethylene and cucurbit[8]uril, SOF-2 is formed by reducing the monomer molecule trimethyl viologen triphenylbenzene with a reducing agent to self-assemble into trimethyl viologen free radical triphenylbenzene and cucurbit[8]uril, and SOF-3 is formed by reducing the monomer molecule tetramethyl viologen tetraphenylporphyrin with a reducing agent to self-assemble into tetramethyl viologen free radical tetraphenylporphyrin and cucurbit[8]uril.

7. Use of the water-soluble transient supramolecular organic framework material prepared by any one of claims 1 to 6 in the field of organic synthesis. 8 . Use of the water-soluble transient supramolecular organic framework material according to claim 7 in an aqueous phase organic synthesis reaction, wherein the aqueous phase organic synthesis reaction is a sulfonation reaction.

9. Use of the water-soluble transient supramolecular organic framework material in a sulfonation reaction according to claim 8, characterized in that: The method for synthesizing a benzyl sulfone compound in an aqueous phase specifically comprises the following steps: Aromatic benzyl bromide and potassium phosphate were added to an aqueous solution containing a methyl viologen derivative and cucurbit[8]uril. After an inert gas was introduced to remove oxygen, a reducing agent was added to drive the formation of a transient supramolecular organic framework material, catalyzing the formation of benzyl sulfone. After the reaction is completed, the transient SOF is disassembled and released into the benzyl sulfone product by exposure to oxygen in the air, and the pure product can be obtained by filtration or extraction.

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