Pyridyl organic bowl-shaped compound and its preparation method and molecular recognition application

Abstract

The present invention discloses a pyridine-based organic bowl-shaped compound, a preparation method thereof, and an application thereof in molecular recognition. The chemical formula of the pyridine-based organic bowl-shaped compound is [C 78 H 69 N 24 ] 9+ 9Cl ‑ , having the structure shown in Formula I below: #imgabs0# This invention utilizes a "multiple covalent bond" stabilization strategy and a heteroatom stabilization strategy to achieve aqueous-compatible imine self-assembly. The cavities of pyridyl-based organic bowl-shaped compounds are electron-deficient. Due to electrostatic attraction and π-π interactions, pyridyl-based organic bowl-shaped compounds can form host-guest complexes with electron-rich guest compounds in aqueous phases, enabling recognition of these electron-rich guest compounds.

Description

Technical Field

[0001] The present invention relates to the field of chemistry, and in particular to a pyridine-based organic bowl-shaped compound, a preparation method thereof, and an application thereof in molecular recognition. Background Art

[0002] Supramolecular chemistry is defined as the study of chemistry at levels above the molecular level. Emerging in the 1960s, it has flourished over the past few decades, becoming a significant branch of chemistry and materials science. Compared to the covalent bonds studied in traditional organic chemistry, supramolecular chemistry focuses on weak intermolecular interactions, such as hydrogen bonding, metal coordination, π-π stacking, hydrophobic effects, and van der Waals forces.

[0003] Molecular recognition is a key area of research in supramolecular chemistry. It is widely present in biological media and plays a vital role, serving as a crucial medium for information storage, replication, and transmission in organisms. For example, molecular recognition occurs between biomolecules such as proteins, sugar chains, and lipids. Within supramolecular chemistry, molecular recognition is a key research area, often achieved by binding two or more molecules together based on weak interactions.

[0004] Over the past few decades, molecular recognition has been primarily accomplished by supramolecular hosts. Generations of supramolecular chemists have developed numerous supramolecular hosts, such as crown ethers, cyclodextrins, cucurbiturils, calixarenes, and pillararenes. Organic bowl-shaped compounds possess open cavities that can accommodate appropriately sized guest molecules. Irreversible bonds and dynamic covalent bonds (Dynamic Covalent Chemistry) are the primary methods for synthesizing supramolecular hosts. Among these, irreversible organic molecular cages are synthesized using amide bonds and nucleophilic aromatic substitution; dynamic covalent bonds (Dynamic Covalent Chemistry) primarily synthesize organic molecular cages through C=N imine bonds and other dynamic covalent bonds.

[0005] Based on reversible chemical processes, organisms are able to efficiently synthesize numerous biomacromolecules with complex structures and remarkable functions. Inspired by this, synthetic chemists have attempted to exploit reversible chemical bonds or forces to allow systems to "self-correct" and find their thermodynamically stable state. This allows product molecules with sufficiently low Gibbs free energy to be synthesized in a one-pot process, avoiding tedious multi-step synthesis and the isolation of by-products, ultimately achieving atom economy in chemical reactions. This dynamic synthesis method is particularly important for synthesizing molecules with numerous building blocks and complex structures. However, artificial self-assembly is far less efficient than biological self-assembly. First, artificial self-assembly is often less precise. Unlike biological self-assembly, which often produces a single target molecule or aggregate, artificial self-assembly is often accompanied by the formation of multiple by-products, resulting in less controllable product structure and composition. Second, unlike biological self-assembly, which occurs in aqueous solutions, artificial self-assembly relies heavily on organic solvents. Artificial host molecules cannot utilize the hydrophobic effect to drive host-guest recognition, thus significantly weakening their object recognition ability, which severely restricts the performance of their supramolecular functions. Thirdly, aqueous solution is the medium of life, and artificial self-assembling molecules with poor compatibility with aqueous solution mean that they have difficulty performing their functions in living systems. Therefore, developing new self-assembly methods and theories, improving the precision of self-assembly, and making the products compatible with aqueous solutions have become the focus of supramolecular chemistry research.

[0006] Since the only by-product of the imine bond formation process is water, the imine condensation reaction is generally not applicable to aqueous solution systems; in response to this traditional technical challenge, how to achieve aqueous solution-compatible imine condensation assembly has become one of the urgent problems to be solved. Summary of the Invention

[0007] The present invention provides a pyridyl-based organic bowl-shaped compound with a large cavity. This compound utilizes a "multiple covalent bond" stabilization strategy and a heteroatom stabilization strategy to achieve aqueous-compatible imine self-assembly. The synthesis method is simple and easy, and the product yield is high. In the application of this pyridyl-based organic bowl-shaped compound in molecular recognition, the cavity of the pyridyl-based organic bowl-shaped compound also has electron-deficient properties, based on the electron-deficient nature of the pyridyl group. Due to electrostatic attraction and π-π interaction forces, the pyridyl-based organic bowl-shaped compound can form a host-guest complex with an electron-rich guest compound in the aqueous phase, thereby achieving recognition of the electron-rich guest compound.

[0008] In the first aspect, a water-soluble pyridyl organic bowl-shaped compound, the chemical formula of which is [C 78 H 69 N 24 ] 9+ 9Cl - , having the structure shown in the following formula I:

[0009]

[0010] In a second aspect, the present invention provides a method for preparing a pyridyl organic bowl-shaped compound:

[0011] a) Compound 1 and Compound 2 are mixed to react to obtain a product having the chemical formula [C 78 H 69 N 24 ] 9+ ·9Br - a pyridyl organic bowl-shaped compound; or

[0012] b) Compound 1 and Compound 2 are mixed and reacted, and ammonium hexafluorophosphate is added to the mixture obtained after the reaction, and mixed evenly, and the solid-liquid separation is performed to obtain a chemical formula of [C 78 H 69 N 24 ] 9+ 9PF6 - a pyridyl organic bowl-shaped compound; or

[0013] c) Based on b), the chemical formula [C 78 H 69 N 24 ] 9+ 9PF6 - The pyridine-based organic bowl-shaped compound is dissolved in an organic solvent, and then a quaternary ammonium salt with a chloride anion is added. After sufficient reaction, the solid-liquid separation is performed to obtain a water-soluble compound after counterion exchange. The chemical formula is [C 78 H 69 N 24 ] 9+ 9Cl - Pyridyl organic bowl-shaped compounds;

[0014] The cation [C 78 H 69 N 24 ] 9+ It has the structure shown in the following formula II:

[0015]

[0016] Preferably, the molar ratio of compound 1 to compound 2 is 3:1.

[0017] Preferably, the temperature for the mixed reaction of compound 1 and compound 2 is 60-100° C., and the time is 5-20 h.

[0018] Preferably, the mixing reaction of compound 1 and compound 2 is carried out in a solvent.

[0019] Preferably, the solvent for the mixed reaction of Compound 1 and Compound 2 includes any one of water, ethanol, dimethyl sulfoxide, and acetone, or a combination of at least two of them.

[0020] Preferably, in the mixed reaction of Compound 1 and Compound 2, the mass ratio of the total mass of Compound 1 and Compound 2 to the solvent is 1:(500-2000).

[0021] Preferably, the mixed reaction of compound 1 and compound 2 is carried out in the presence of an acid catalyst;

[0022] Preferably, the acid catalyst includes any one of trifluoroacetic acid, trifluoromethanesulfonic acid, acetic acid, and hydrochloric acid, or a combination of at least two thereof.

[0023] Preferably, in the mixed reaction of compound 1 and compound 2, the volume ratio of the acid catalyst to the solvent is 1:(10-100).

[0024] Preferably, the molar ratio of ammonium hexafluorophosphate to compound 2 is not less than 9:1.

[0025] Preferably, the temperature of adding ammonium hexafluorophosphate and mixing is 25-35° C. and the time is 5-20 minutes;

[0026] Preferably, the solid-liquid separation in b) is vacuum filtration.

[0027] Preferably, the organic solvent in c) is at least one of acetonitrile, acetone, tetrahydrofuran and methanol.

[0028] Preferably, the quaternary ammonium salt in c) is in molar amount of the anion chloride ion it contains and the chemical formula is [C 78 H 69 N 24 ] 9+ 9PF6 - The molar ratio of the pyridyl organic bowl-shaped compound is not less than 9:1.

[0029] Preferably, the quaternary ammonium salt in c) and the chemical formula are [C 78 H 69 N 24 ] 9+ 9PF6 - The mass ratio of the sum of the masses of the pyridyl organic bowl-shaped compound to the mass ratio of the organic solvent is 1:(50-2000).

[0030] Preferably, the temperature for the sufficient reaction in c) is 25-35° C., and the time is 5-20 min.

[0031] Preferably, the solid-liquid separation in c) is vacuum filtration.

[0032] Compound 1 can be prepared by reacting 4-hydrazinopyridine with acetone and dibromomethane.

[0033] Preferably, the molar ratio of dibromomethane to 4-hydrazinopyridine is not less than 1:2.

[0034] Preferably, the molar ratio of acetone to 4-hydrazinopyridine is not less than 1:1.

[0035] Preferably, the temperature for the reaction of 4-hydrazinopyridine, acetone and dibromomethane is 55-65° C. and the time is 5-120 h.

[0036] Preferably, the mixed reaction of 4-hydrazinopyridine with acetone and dibromomethane is carried out in the presence of a protective gas.

[0037] Preferably, in the preparation of compound 1, the protective gas is at least one of nitrogen and a rare gas.

[0038] Preferably, the mixed reaction of 4-hydrazinopyridine, acetone and dibromomethane is carried out in a solvent.

[0039] Preferably, in the preparation of compound 1, the solvent includes any one or a combination of at least two of acetone, acetonitrile, dimethyl sulfoxide, and 1,4-dioxane.

[0040] Preferably, in the preparation of compound 1, the mass ratio of the sum of the masses of 4-hydrazinopyridine and dibromomethane to the mass of the solvent is 1:(5-200).

[0041] Preferably, after the reaction of 4-hydrazinopyridine with acetone and dibromomethane, the solid-liquid separation and drying of the reaction mixture are performed.

[0042] Compound 2 can be prepared by reacting 5-(bromomethyl)isophthalaldehyde with 2,4,6-tris(4-pyridyl)-1,3,5-triazine.

[0043] Preferably, the molar ratio of 5-(bromomethyl)isophthalaldehyde to 2,4,6-tris(4-pyridyl)-1,3,5-triazine is not less than 3:1.

[0044] Preferably, the temperature for the mixed reaction of 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine is 60-100° C., and the time is 12-240 hours.

[0045] Preferably, the mixed reaction of 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine is carried out in the presence of a protective gas.

[0046] Preferably, in the preparation of compound 2, the protective gas is at least one of nitrogen and a rare gas.

[0047] Preferably, the mixed reaction of 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine is carried out in a solvent.

[0048] Preferably, in the preparation of compound 2, the solvent includes any one or a combination of at least two of acetone, acetonitrile, dimethyl sulfoxide, and 1,4-dioxane.

[0049] Preferably, in the preparation of compound 2, the mass ratio of the sum of the masses of 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine to the solvent is 1:(5-200).

[0050] Preferably, after the mixed reaction of 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine, the solid-liquid separation and drying of the reaction mixture are performed.

[0051] In a third aspect, the present invention provides a use of the water-soluble pyridyl organic bowl-shaped compound according to the first aspect in molecular recognition.

[0052] In one embodiment, the application is carried out in an aqueous phase, and the water-soluble pyridine-based organic bowl-shaped compound has an electron-deficient property. Due to electrostatic attraction and π-π interaction, the water-soluble pyridine-based organic bowl-shaped compound can form a host-guest complex with an electron-rich guest compound in an aqueous phase, thereby realizing the recognition of the electron-rich guest compound.

[0053] Furthermore, the electron-rich guest compound may be a (S)-spirodiphenol phosphate or a water-soluble salt whose anion is a closed carborane anion;

[0054] (S)-Spirocyclic diphenol phosphate is compound 4:

[0055]

[0056] The closed carborane anion has the structure shown in Formula III below:

[0057]

[0058] In one embodiment, the water-soluble salt of the closed carborane anion is compound 3:

[0059]

[0060] In a fourth aspect, the present invention provides a method for molecular recognition using a pyridyl organic bowl-shaped compound, wherein the pyridyl organic bowl-shaped compound and a molecule to be identified are dissolved in heavy water and allowed to stand. The resulting mixed solution is analyzed by nuclear magnetic resonance proton spectroscopy. If the nuclear magnetic shift changes, it indicates that the molecule to be identified is a guest molecule that has entered the cage cavity of the pyridyl organic bowl-shaped compound and has been identified.

[0061] The chemical formula of the pyridyl organic bowl-shaped compound is [C 78 H 69 N 24 ] 9+ 9Cl - , having the structure shown in the following formula I:

[0062]

[0063] Compared with the prior art, the present invention has the following beneficial effects:

[0064] 1. The pyridyl organic bowl-shaped compound of the present invention can be prepared by an imine condensation reaction in an aqueous solution. The synthesis method is simple and easy, and the product yield is high.

[0065] 2. The cations in the pyridyl organic bowl-shaped compound of the present invention are interconnected by covalent bonds and have good chemical stability and thermal stability.

[0066] 3. The pyridyl organic bowl-shaped compound described in the present invention is composed of light elements and does not contain metal elements.

[0067] 4. The pyridyl organic bowl-shaped compound of the present invention is easy to purify and can be made water-soluble through anion exchange, which is conducive to further research on subsequent compatibility applications in biological systems.

[0068] 5. The cations in the pyridyl organic bowl-shaped compounds of the present invention carry a high positive charge and can form host-guest complexes with electron-deficient guest compounds in aqueous solution by utilizing electrostatic attraction and CH-π interaction forces, and are used to identify electron-deficient guest compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the pyridyl organic bowl-shaped compound provided in Example 1;

[0070] Figure 2 This is the mass spectrum of the pyridyl organic bowl-shaped compound provided in Example 1;

[0071] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the pyridyl organic bowl-shaped compound provided in Example 2;

[0072] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum obtained in Example 3;

[0073] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum obtained in Example 4;

[0074] Figure 6 This is a graph showing the binding constants of the pyridyl organic bowl-shaped compound of Example 3 and Compound 3;

[0075] Figure 7 This is a diagram of the binding constants of the pyridyl organic bowl-shaped compound of Example 4 and Compound 4. DETAILED DESCRIPTION

[0076] The present invention will be further described below with reference to the accompanying drawings and specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0077] Example 1

[0078] This embodiment provides a method for preparing a pyridyl organic bowl-shaped compound, comprising the following steps: (1)

[0080]

[0081] 4-Hydrazinopyridine (2.0 g, 18.3 mmol) and acetone (400 mL) were mixed and reacted at 60°C under a nitrogen atmosphere for 12 h. Dibromomethane (3 g, 17.3 mmol) was added and the reaction was continued for 12 h. After the reaction, the mixture was filtered and dried to obtain an off-white solid, Compound 1, in a yield of 35%. 1 H NMR (400MHz, D2O) δ8.34 (d, J = 8Hz, 2H), 8.25 (d, J = 8Hz, 2H), 7.42 (dd, J = 8, 2.6Hz, 2H), 7.07 (dd, J = 8, 2.7Hz, 2H), 6.40 (s, 2H), 2.10 (d, J = 25Hz, 12H). (2)

[0083]

[0084] 2,4,6-Tris(4-pyridyl)-1,3,5-triazine (50 mg, 0.16 mmol), 5-(bromomethyl)isophthalaldehyde (363 mg, 1.6 mmol) and acetonitrile (25 mL) were mixed and reacted at 90° C. under a nitrogen atmosphere for 7 days. After the reaction, the mixture obtained after the reaction was filtered and dried to obtain a brown solid, namely, compound 2, with a yield of 83%. 1H NMR (400MHz, 298K, DMSO-d6) δ = 10.15 (s, 6H), 9.76 (d, J = 7Hz, 6H), 9.58 (d, J = 7Hz, 6H), 8.55 (s, 3H), 8.51 (s, 6H), 6.29 (s, 6H). (3)

[0086]

[0087] Compound 1 (42.5 mg, 0.09 mmol), compound 2 (29.8 mg, 0.03 mmol), trifluoroacetic acid (TFA, 2 mL) and water (100 mL) were mixed and reacted at 80°C for 12 hours. After the reaction was completed, ammonium hexafluorophosphate (163 mg, 1 mmol) was added to the mixture obtained after the reaction and mixed at 25-35°C for 10 minutes. The mixture was filtered under reduced pressure to obtain a pyridyl organic bowl-shaped compound B. 1 H NMR (500MHz, CD3CN): δ = 11.86 (s, 4H), 9.54 (d, J = 6Hz, 6H), 9.43 (d, J = 6Hz, 6H), 8.64–8.60 (m, 6H), 8.57 (dd, J = 7, 2Hz, 6H), 8.32 (dd, J = 7, 2Hz, 7H), 8.2 9(s,6H),7.97(dd,J=8,3Hz,6H),7.66(s,3H),7.16(dd,J=7,3Hz,6H),6.50 (d,J=14Hz,3H),6.35(d,J=14Hz,3H),5.96(s,6H).ESI-HRMS:[M-2H+2PF6] 5+ ,observed:m / z 325.9041,calculated:m / z325.9047;[M-H+3PF6] 5+ ,observed:m / z 355.0991,calculated:m / z 355.0991;[M-2H+3PF6] 4+ ,observed:m / z 443.6238,calculated:m / z 443.6221;[M+5PF6] 4+ ,observed:m / z516.6107,calculated:m / z 516.6081;[M-3H+3PF6] 3+ ,observed:m / z 591.1617,calculated:m / z 591.1604;[M-H+5PF6] 3+,observed:m / z 688.4800,calculated:m / z688.4751;[M+6PF6] 3+ , observed: m / z 737.1478, calculated: m / z 737.1324.

[0088] Pyridyl organic bowl-shaped compound B 1 The results of H NMR detection are as follows Figure 1 The mass spectrometry results are shown in Figure 2 shown.

[0089] Example 2

[0090] Counterion exchange of pyridyl organic bowl-shaped compounds:

[0091] The pyridyl organic bowl-shaped compound B (16.6 mg, 0.01 mmol) prepared in Example 1 was dissolved in 50 mL of acetonitrile, and tetrabutylammonium chloride (27.8 mg, 0.1 mmol) was added. The mixture was allowed to stand at 25°C for 10 min and filtered under reduced pressure to obtain a pyridyl organic bowl-shaped compound A that is soluble in water; the compound can be directly dissolved in water for molecular recognition.

[0092]

[0093] Pyridyl organic bowl-shaped compound A 1 The results of H NMR detection are as follows Figure 3 shown.

[0094] Example 3

[0095] Molecular recognition of compound 3 and its anion by pyridyl organic bowl-shaped compound A.

[0096]

[0097] The pyridyl organic bowl-shaped compound A (16.6 mg, 0.01 mmol) prepared in Example 2 was mixed with heavy water (10 mL) to prepare a solution of the pyridyl organic bowl-shaped compound A with a concentration of 1 mM.

[0098] 4.5 mL of the solution of the pyridyl organic bowl-shaped compound A was transferred to a sample bottle, and a certain mass of compound 3 was weighed and added to the sample bottle containing 4.5 mL of the pyridyl organic bowl-shaped compound A to prepare a solution of compound 3 of a certain concentration.

[0099] Pipette 500 μL of the solution of pyridyl organic bowl-shaped compound A into the NMR tube, and gradually add a certain concentration of compound 3 solution into the NMR tube of 500 μL of the solution of pyridyl organic bowl-shaped compound A to complete the 1H NMR titration was performed to record the concentration of compound 3 and the shift change of its NMR peak.

[0100] 1 The results of H NMR titration are as follows Figure 4 The binding constant test results are shown in Figure 6 shown.

[0101] 1 H NMR titration showed that the nuclear magnetic shift of pyridyl organic bowl-shaped compound A changed significantly, indicating that pyridyl organic bowl-shaped compound A had a host-guest interaction with guest molecule compound 3. After fitting, the value of the binding constant was (3.6±0.2)×10 2 M -1 , indicating that the pyridine organic bowl-shaped compound A can effectively recognize the guest molecule compound 3 in aqueous solution.

[0102] Example 4

[0103] Molecular recognition of compound 4 by pyridyl organic bowl-shaped compound A.

[0104]

[0105] The pyridyl organic bowl-shaped compound A (16.6 mg, 0.01 mmol) prepared in Example 2 was mixed with heavy water (10 mL) to prepare a solution of the pyridyl organic bowl-shaped compound A with a concentration of 1 mM.

[0106] 4.5 mL of the solution of the pyridyl organic bowl-shaped compound A was transferred to a sample bottle, and a certain mass of compound 4 was weighed and added to the sample bottle containing 4.5 mL of the pyridyl organic bowl-shaped compound A to prepare a solution of compound 4 at a certain concentration.

[0107] Pipette 500 μL of the solution of pyridyl organic bowl-shaped compound A into the NMR tube, and gradually add a certain concentration of compound 4 solution into the NMR tube of 500 μL of the solution of pyridyl organic bowl-shaped compound A to complete the 1 H NMR titration was performed to record the concentration of compound 4 and the shift change of its NMR peak.

[0108] 1 The results of H NMR titration are as follows Figure 5 The binding constant test results are shown in Figure 7 shown.

[0109] 1H NMR titration showed that the nuclear magnetic shift of pyridyl organic bowl-shaped compound A changed significantly, indicating that pyridyl organic bowl-shaped compound A had a host-guest interaction with guest molecule compound 4. After fitting, the value of the binding constant was (1.0±0.1)×10 5 M -1 , indicating that the pyridine organic bowl-shaped compound A can effectively recognize the guest molecule compound 4 in aqueous solution.

[0110] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. A water-soluble pyridyl organic bowl-shaped compound, characterized in that The chemical formula is [C 78 H 69 N 24 ] 9+ 9Cl - , having the structure shown in the following formula I:

2. A method for preparing a pyridyl organic bowl-shaped compound, characterized in that: a) Compound 1 and Compound 2 are mixed to react to obtain a product having the chemical formula [C 78 H 69 N 24 ] 9+ ·9Br - a pyridyl organic bowl-shaped compound; or b) Compound 1 and Compound 2 are mixed and reacted, and ammonium hexafluorophosphate is added to the mixture obtained after the reaction, and mixed evenly, and the solid-liquid separation is performed to obtain a chemical formula of [C 78 H 69 N 24 ] 9+ 9PF6 - a pyridyl organic bowl-shaped compound; or c) Based on b), the chemical formula [C 78 H 69 N 24 ] 9+ 9PF6 - The pyridine-based organic bowl-shaped compound is dissolved in an organic solvent, and then a quaternary ammonium salt with a chloride anion is added. After sufficient reaction, the solid-liquid separation is performed to obtain a water-soluble compound after counterion exchange. The chemical formula is [C 78 H 69 N 24 ] 9+ 9Cl - Pyridyl organic bowl-shaped compounds; The cation [C 78 H 69 N 24 ] 9+ It has the structure shown in the following formula II:

3. The preparation method according to claim 2, characterized in that The molar ratio of compound 1 to compound 2 is 3:

1.

4. The preparation method according to claim 2, characterized in that The temperature for the mixed reaction of compound 1 and compound 2 is 60-100° C., and the time is 5-20 h.

5. The preparation method according to claim 2, characterized in that The mixed reaction of compound 1 and compound 2 is carried out in a solvent.

6. The preparation method according to claim 5, characterized in that The solvent for the mixed reaction of compound 1 and compound 2 includes any one of water, ethanol, dimethyl sulfoxide, and acetone, or a combination of at least two of them.

7. The preparation method according to claim 5 or 6, characterized in that: In the mixed reaction of compound 1 and compound 2, the mass ratio of the total mass of compound 1 and compound 2 to the solvent is 1:(500-2000).

8. The preparation method according to claim 5, characterized in that The mixed reaction of compound 1 and compound 2 is carried out in the presence of an acid catalyst.

9. The preparation method according to claim 8, characterized in that The acid catalyst includes any one of trifluoroacetic acid, trifluoromethanesulfonic acid, acetic acid, and hydrochloric acid, or a combination of at least two thereof.

10. The preparation method according to claim 8 or 9, characterized in that: In the mixed reaction of compound 1 and compound 2, the volume ratio of the acid catalyst to the solvent is 1:(10-100).

11. The preparation method according to claim 2, characterized in that The molar ratio of the ammonium hexafluorophosphate to the compound 2 is not less than 9:

1.

12. The preparation method according to claim 2, characterized in that The temperature for adding ammonium hexafluorophosphate and mixing is 25-35° C. and the time is 5-20 minutes.

13. The preparation method according to claim 2, characterized in that b) The solid-liquid separation is vacuum filtration.

14. The preparation method according to claim 2, characterized in that The organic solvent in c) is at least one of acetonitrile, acetone, tetrahydrofuran and methanol.

15. The preparation method according to claim 2, characterized in that c) the quaternary ammonium salt is measured by the molar amount of the anion chloride ion it contains and the chemical formula is [C 78 H 69 N 24 ] 9+ 9PF6 - The molar ratio of the pyridyl organic bowl-shaped compound is not less than 9:

1.

16. The preparation method according to claim 2, characterized in that c) the quaternary ammonium salt and the chemical formula [C 78 H 69 N 24 ] 9+ 9PF6 - The mass ratio of the sum of the masses of the pyridyl organic bowl-shaped compound to the mass ratio of the organic solvent is 1:(50-2000).

17. The preparation method according to claim 2, characterized in that The temperature of the sufficient reaction in c) is 25-35° C. and the time is 5-20 min.

18. The preparation method according to claim 2, characterized in that The solid-liquid separation in c) is vacuum filtration.

19. The preparation method according to claim 2, characterized in that: Compound 1 is prepared by reacting 4-hydrazinopyridine with acetone and dibromomethane.

20. The preparation method according to claim 19, characterized in that The molar ratio of dibromomethane to 4-hydrazinopyridine is not less than 1:

2.

21. The preparation method according to claim 19, characterized in that The molar ratio of acetone to 4-hydrazinopyridine is not less than 1:

1.

22. The preparation method according to claim 19, characterized in that The temperature for the mixed reaction of 4-hydrazinopyridine, acetone and dibromomethane is 55-65° C. and the reaction time is 5-120 hours.

23. The preparation method according to claim 19, characterized in that The mixed reaction of 4-hydrazinopyridine with acetone and dibromomethane is carried out in the presence of a protective gas.

24. The preparation method according to claim 23, characterized in that In the preparation of compound 1, the protective gas is at least one of nitrogen and a rare gas.

25. The preparation method according to claim 19, characterized in that The mixed reaction of 4-hydrazinopyridine, acetone and dibromomethane is carried out in a solvent.

26. The preparation method according to claim 25, characterized in that In the preparation of compound 1, the solvent includes any one of acetone, acetonitrile, dimethyl sulfoxide, and 1,4-dioxane, or a combination of at least two thereof.

27. The preparation method according to claim 25 or 26, characterized in that: In the preparation of compound 1, the mass ratio of the sum of the masses of 4-hydrazinopyridine and dibromomethane to the mass of the solvent is 1:(5-200).

28. The preparation method according to claim 19, characterized in that After 4-hydrazinopyridine is mixed with acetone and dibromomethane for reaction, the solid-liquid separation and drying of the reaction mixture are performed.

29. The preparation method according to claim 2, characterized in that Compound 2 is prepared by reacting 5-(bromomethyl)isophthalaldehyde with 2,4,6-tris(4-pyridyl)-1,3,5-triazine.

30. The preparation method according to claim 29, characterized in that The molar ratio of 5-(bromomethyl)isophthalaldehyde to 2,4,6-tris(4-pyridyl)-1,3,5-triazine is not less than 3:

1.

31. The preparation method according to claim 29, characterized in that The temperature for the mixed reaction of 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine is 60-100° C. and the time is 12-240 hours.

32. The preparation method according to claim 29, characterized in that The mixed reaction of 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine is carried out in the presence of protective gas.

33. The preparation method according to claim 32, characterized in that In the preparation of compound 2, the protective gas is at least one of nitrogen and a rare gas.

34. The preparation method according to claim 29, characterized in that The mixed reaction of 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine is carried out in a solvent.

35. The preparation method according to claim 34, characterized in that In the preparation of compound 2, the solvent includes any one of acetone, acetonitrile, dimethyl sulfoxide, and 1,4-dioxane, or a combination of at least two thereof.

36. The preparation method according to claim 34 or 35, characterized in that In the preparation of compound 2, the mass ratio of the sum of the masses of 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine to the solvent is 1:(5-200).

37. The preparation method according to claim 29, characterized in that After 5-(bromomethyl)isophthalaldehyde and 2,4,6-tris(4-pyridyl)-1,3,5-triazine are mixed and reacted, the solid-liquid separation and drying of the reaction mixture are performed.

38. Use of the water-soluble pyridyl organic bowl-shaped compound in molecular recognition according to claim 1, characterized in that: The application is carried out in an aqueous phase. The water-soluble pyridyl organic bowl-shaped compound has an electron-deficient property. Due to electrostatic attraction and π-π interaction, the water-soluble pyridyl organic bowl-shaped compound can form a host-guest complex with an electron-rich guest compound in an aqueous phase, thereby realizing the recognition of the electron-rich guest compound. The electron-rich guest compound is (S)-spirodiphenol phosphate or a water-soluble salt whose anion is a closed carborane anion. (S)-Spirocyclic diphenol phosphate is compound 4: The water-soluble salt of the closed carborane anion is compound 3:

39. A method for molecular recognition using a pyridyl organic bowl-shaped compound, characterized in that: The pyridyl organic bowl-shaped compound and the molecule to be identified are dissolved in heavy water and allowed to stand. The resulting mixed solution is analyzed by nuclear magnetic resonance (HNMR). If the nuclear magnetic shift changes, it indicates that the molecule to be identified is a guest molecule that has entered the cage cavity of the pyridyl organic bowl-shaped compound and has been identified. The chemical formula of the pyridyl organic bowl-shaped compound is [C 78 H 69 N 24 ] 9+ 9Cl - , having the structure shown in the following formula I: The molecule to be identified is (S)-spirodiphenol phosphate or a water-soluble salt whose anion is a closed carborane anion; (S)-Spirocyclic diphenol phosphate is compound 4: The water-soluble salt of the closed carborane anion is compound 3:

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