Triazinyl organic molecular cage capable of being produced on large scale and synthesis method thereof

Abstract

The invention discloses a triazinyl organic molecular cage capable of being produced on a large scale and a synthesis method thereof, and relates to the technical field of organic materials, and the organic molecular cage is prepared from a bis / trifunctional compound and cyanuric chloride in an organic solvent under the catalytic action of a basic catalyst. The method comprises the following steps: accurately weighing an organic solvent and cyanuric chloride, and preparing an organic solvent solution of cyanuric chloride; the preparation method comprises the following steps: adding an accurately weighed bis / trifunctional compound and a basic catalyst into a reactor, slowly dropwise adding an organic solvent solution of cyanuric chloride while stirring under an ice-water bath condition, and stirring and reacting for 24 hours at 10-100 DEG C after dropwise adding; after the reaction is finished, performing suction filtration to obtain a triazine organic molecular cage crude product; and respectively washing the obtained crude product twice with methanol, dichloromethane and water, and carrying out vacuum drying at 40 DEG C for 4 hours to obtain a powdery triazinyl organic molecular cage product. The prepared organic molecular cage is low in cost, high in chemical stability, simple in production process, very high in operability and practicability, suitable for large-scale production and wide in application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of organic materials, in particular to a triazine-based organic molecular cage that can be produced on a large scale and a synthesis method thereof. Background Art

[0002] In recent years, a new class of porous materials with discrete structures—porous organic molecular cages—has gradually emerged. They possess excellent solubility and can assemble and stack to form ordered crystalline assemblies through weak interactions (such as van der Waals forces and dipole-dipole interactions). Their advantages include low skeletal density, high specific surface area, and excellent chemical stability, attracting increasing attention in fields such as gas adsorption and separation, molecular recognition, and catalysis. In 2009, Professor Andrew I. Cooper reported the first organic porous molecular cage (Nat. Mater., 2009, 8, 973), ushering in a new chapter in the research of this class of materials. Over the past decade, organic molecular cages have continued to develop. Chemists have designed and synthesized various organic molecular cages through various chemical reactions, such as imine condensation, boronic acid condensation, and olefin / alkyne metathesis. However, the monomers for these organic molecular cages are generally expensive, which increases the cost of their synthesis and makes their commercial application more difficult. To date, no manufacturer in China or abroad has mass-produced organic molecular cages. Summary of the Invention

[0003] The technical problem addressed by this invention is to overcome existing deficiencies by providing a molecular cage containing heteroatoms (N, O, and S) prepared by nucleophilic substitution reaction between cyanuric chloride and di- / trifunctional compounds. The low cost of cyanuric chloride and di- / trifunctional compounds fundamentally reduces the production cost of triazine-based organic molecular cages, making their industrialization feasible. The introduction of heteroatoms enables the synthesized triazine-based organic molecular cages to be widely used in fields such as molecular recognition, gas adsorption and separation, and catalyst supports.

[0004] To achieve the above objectives, the first technical solution of the present invention protects a triazine-based organic molecular cage that can be produced on a large scale. The organic molecular cage is prepared by a di / trifunctional compound and cyanuric chloride in the presence of an alkaline catalyst.

[0005] Furthermore, the bifunctional compound is one of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, ethanedithiol, butylenethiol, and hexamethylenethiol; the trifunctional compound is one of tris(2-aminoethyl)amine and triethanolamine.

[0006] Furthermore, the alkaline catalyst is one of triethylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, Na2CO3, K2CO3, and Cs2CO3.

[0007] Furthermore, the composition ratio of the bifunctional compound to cyanuric chloride in the molecular cage structure is [6+4], and the composition ratio of the trifunctional compound to cyanuric chloride is [4+4].

[0008] Furthermore, the organic solvent includes one of tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, acetonitrile, and dimethyl sulfoxide.

[0009] Another technical aspect protected by the present invention is a method for synthesizing triazine-based organic molecular cages that can be produced on a large scale. The synthesis steps are as follows:

[0010] (1) accurately weighing an organic solvent and cyanuric chloride, stirring and mixing, and forming an organic solvent solution of cyanuric chloride;

[0011] (2) Add accurately weighed difunctional / trifunctional compound and alkaline catalyst to the reactor, slowly add the organic solvent solution of cyanuric chloride dropwise while stirring in an ice-water bath, and stir and react at 10-100° C. for 24 hours after the addition is complete;

[0012] (3) After the reaction is completed, the crude triazine organic molecular cage product is obtained by filtration;

[0013] (4) The crude product was washed twice with methanol, dichloromethane and water respectively, and dried in a vacuum oven at 40°C for 4 hours to obtain a powdered triazine organic molecular cage.

[0014] Compared with the prior art, the triazine-based organic molecular cage and its synthesis method that can be produced on a large scale protected by the present invention have the following advantages:

[0015] 1. The organic molecular cage protected by the present invention is a heteroatom-containing molecular cage prepared by a nucleophilic substitution reaction between cyanuric chloride and a di- / trifunctional compound. The low price of cyanuric chloride and di- / trifunctional compounds fundamentally reduces the production cost of triazine molecular cages, making their industrialization possible;

[0016] 2. The introduction of heteroatoms (N, O, and S) provides more active sites, which can make the synthesized triazine molecular cage widely used in the fields of molecular recognition, gas adsorption and separation, catalyst support, etc.

[0017] 3. The raw materials required for this synthesis method are cheap, the preparation process is simple, the operation is easy, the yield is high, and the obtained organic molecular cage has high chemical stability, strong operability and practicality, is suitable for large-scale production, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 A roadmap for the synthesis of triazine molecular cages using bifunctional compounds and cyanuric chloride as raw materials, where the molecules self-assemble to form [4+6] type organic molecular cages;

[0019] Figure 2 A roadmap for the synthesis of triazine molecular cages using trifunctional compounds and cyanuric chloride as raw materials, where the molecules self-assemble to form [4+4] type organic molecular cages;

[0020] Figure 3 The XRD patterns of ethylenediamine organic molecular cages synthesized at different temperatures;

[0021] Figure 4 XRD patterns of triethanolamine molecular cage and tris(2-aminoethyl)amine molecular cage; DETAILED DESCRIPTION

[0022] The following will be combined with the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0023] Example 1:

[0024] To a reaction flask, add ethylenediamine (0.03 mol), triethylamine (0.06 mol), and 100 mL of 1,4-dioxane. A solution of cyanuric chloride (0.02 mol) in 1,4-dioxane (40 mL) is slowly added dropwise with stirring in an ice-water bath. After the addition is complete, the mixture is allowed to react at room temperature for 2 hours, then heated to 10°C and stirred for 24 hours. Upon completion of the reaction, the crude EDTA molecular cage is filtered and washed twice with methanol, dichloromethane, and water, respectively. The mixture is then vacuum-dried at 40°C for 4 hours to obtain a powdered EDTA molecular cage with a yield of 83%.

[0025] Example 2:

[0026] Butanediol (0.03 mol), potassium carbonate (0.03 mol), and 100 mL of N,N-dimethylformamide were added to a reaction flask. A solution of cyanuric chloride (0.02 mol) in N,N-dimethylformamide (40 mL) was slowly added dropwise with stirring in an ice-water bath. After the addition was complete, the mixture was allowed to react at room temperature for 2 hours, then heated to 100°C and stirred for 24 hours. The crude butanediol triazine molecular cages were filtered and then washed twice with methanol, dichloromethane, and water, respectively. The resulting powdered butanediol triazine molecular cages were dried under vacuum at 40°C for 4 hours, yielding a 78% yield.

[0027] Example 3:

[0028] To a reaction flask, tris(2-aminoethyl)amine (0.02 mol), cesium carbonate (9.77 g, 0.03 mol), and acetonitrile (100 mL) were added. A solution of cyanuric chloride (0.02 mol) in acetonitrile (40 mL) was slowly added dropwise with stirring in an ice-water bath. After the addition was complete, the mixture was allowed to react at room temperature for 2 hours, then heated to 80°C and stirred for 24 hours. After the reaction was complete, the crude tris(2-aminoethyl)amine triazine molecular cage was filtered and washed twice with methanol, dichloromethane, and water, respectively. The mixture was then dried under vacuum at 40°C for 4 hours to obtain a powdered tris(2-aminoethyl)amine triazine molecular cage in a yield of 68%.

[0029] In the embodiments of the present invention, triazine-based organic molecular cages were designed and synthesized for the first time using cyanuric chloride and di / trifunctional compounds as raw materials. The cheap raw materials make the industrialization of triazine organic molecular cages possible.

[0030] Table 1 Comparison of synthesis costs of organic molecular cages

[0031]

[0032] Depend on Figure 3 It can be seen that the ethylenediamine molecular cage exhibits a high degree of crystallinity and order; Figure 4 It can be seen that both the triethanolamine molecular cage and the tris(2-aminoethyl)amine molecular cage exhibit high crystallinity and order.

[0033] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention's description and drawings, or any direct or indirect application of other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A triazine-based organic molecular cage that can be mass-produced, characterized by: The organic molecular cage is prepared by reacting a difunctional / trifunctional compound with cyanuric chloride in an organic solvent under the catalytic action of an alkaline catalyst.

2. The triazine-based organic molecular cage that can be mass-produced according to claim 1, characterized in that: The bifunctional compound is one of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, ethanedithiol, butylenethiol, and hexamethylenethiol.

3. The triazine-based organic molecular cage that can be mass-produced according to claim 1, characterized in that: The trifunctional compound is one of tris(2-aminoethyl)amine and triethanolamine.

4. A triazine-based organic molecular cage that can be mass-produced according to claim 2, characterized in that The composition ratio of the bifunctional compound to cyanuric chloride in the molecular cage structure is [6+4], and the composition ratio of the trifunctional compound to cyanuric chloride is [4+4].

5. The triazine-based organic molecular cage that can be mass-produced according to claim 3, characterized in that: The alkaline catalyst is one of triethylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, Na2CO3, K2CO3, and Cs2CO3.

6. The triazine-based organic molecular cage that can be mass-produced according to claim 1, characterized in that: The organic solvent includes one of tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, acetonitrile and dimethyl sulfoxide.

7. A method for synthesizing a triazine-based organic molecular cage that can be mass-produced according to any one of claims 1 to 6, characterized in that The synthesis steps are as follows: (1) Accurately weigh 20 mL of an organic solvent and 0.02 mol of cyanuric chloride to prepare an organic solvent solution of cyanuric chloride; (2) Add 0.03 mol of a bifunctional compound and 0.06 mol of a basic catalyst to a reactor, slowly dropwise add a solution of cyanuric chloride in an organic solvent while stirring in an ice-water bath, and stir and react at 10-100° C. for 24 hours after the addition is complete; (3) After the reaction is completed, the crude triazine organic molecular cage product is obtained by filtration; (4) The crude product was washed twice with methanol, dichloromethane and water respectively, and dried in a vacuum oven at 40°C for 4 hours to obtain a powdered triazine organic molecular cage.

8. The method for synthesizing a triazine-based organic molecular cage that can be mass-produced according to claim 7, characterized in that The synthesis steps are as follows: (1) Accurately weigh 20 mL of an organic solvent and 0.02 mol of cyanuric chloride to prepare an organic solvent solution of cyanuric chloride; (2) Add 0.02 mol of a trifunctional compound and 0.06 mol of a basic catalyst to a reactor, slowly add a solution of cyanuric chloride in an organic solvent dropwise while stirring in an ice-water bath, and stir and react at 10-100° C. for 24 hours after the addition is complete; (3) After the reaction is completed, the crude triazine organic molecular cage product is obtained by filtration; (4) The crude product was washed twice with methanol, dichloromethane and water respectively, and dried in a vacuum oven at 40°C for 4 hours to obtain a powdered triazine organic molecular cage.

Images