A hetero[4]aromatic macrocyclic compound and its preparation method and application

Abstract

The present invention relates to a hetero[4]aromatic macrocyclic compound and a preparation method and application thereof, and belongs to the field of compound synthesis. A hetero[4]aromatic macrocyclic compound, the compound having a structure of the following general formula I: The hetero[4]aromatic macrocyclic compound is prepared by the following method: first, ethyl bromide and 2,6-dihydroxynaphthalene are reacted to obtain an intermediate product; the intermediate product, 1,3-dimethoxybenzene and polyformaldehyde are reacted under the catalysis of trifluoroacetic acid, and then column chromatography is performed to obtain the product. The trifluoroacetic acid catalytic system of the present invention is easy to operate, has mild reaction conditions, is fast, and has a high conversion rate. The synthesized hetero[4]aromatic of the present invention has potential application prospects in the purification of petrochemical raw materials and the like. The synthesized hetero[4]aromatic of the present invention can efficiently complex silver ions, thereby achieving the purpose of identification.

Description

Technical Field

[0001] The present invention relates to a hetero[4]arene macrocyclic compound and a preparation method and application thereof, belonging to the field of compound synthesis. Background Art

[0002] Since the birth of supramolecular chemistry, the synthesis of supramolecular macrocyclic receptors with novel structures and good host-guest properties has been a persistent research direction for supramolecular chemists. Following the discovery and development of star macrocyclic molecules based on crown ethers, cyclodextrins, calixarene, cucurbituril, and pillararene, a series of macrocyclic molecules with novel structures and excellent physical and chemical properties have been synthesized and reported. However, most of the current supramolecular macrocycles are composed of the same building blocks, which limits their further application in many fields. Integrating two or more different types of units into a macrocycle can selectively introduce multiple functional groups, which undoubtedly promotes the development of macrocyclic host molecules with different shapes, cavity sizes, and flexibility. Recently, Szumna and colleagues constructed a series of cyclic phenol oligomer compounds composed of different alkoxybenzene units and named them "hybrid[n]arenes". Yu Guocan and colleagues constructed the synthesis of [2]calix[1]biphenyl-type hybrid[3]arenes, opening up a new route for the synthesis of heteroarenes, which can be further used in many fields of supramolecular chemistry.

[0003] The patent specification with publication number CN 107986946 A discloses a method for synthesizing supramolecular macrocyclic receptor-extended column [6] aromatic hydrocarbons. All the synthetic methods have the characteristics of simple operation, easy availability of raw materials and reagents, mild conditions, few reaction steps, simple post-treatment, easy separation and purification of products, and high yield. They are suitable for synthesizing a variety of fully functional extended column [6] aromatic hydrocarbon derivatives and are expected to achieve commercial industrialization.

[0004] The patent specification with the publication number CN 115594648 A discloses a method for synthesizing nitrogen heterocyclic compounds by directional alkylation, which solves the problem that the directional alkylation of existing saturated nitrogen heteroaromatic compounds requires the participation of some protecting groups and coupling reagents, and requires harsh high temperature reaction conditions. Directed alkylated nitrogen heterocyclic compounds can be obtained by a simple method.

[0005] In recent years, due to the actual needs of production, the requirements for the purity of the final product have been greatly improved, but the cumbersome synthesis steps and harsh reaction conditions have reduced the yield of the final product. In addition, some supramolecular macrocyclic derivatives are difficult to prepare and the functional groups are difficult to react, which reduces their application areas. Summary of the invention

[0006] In view of the deficiencies in the art, the present invention has developed and created a new class of macrocyclic molecular compounds based on the summary of the disadvantages and shortcomings of existing supramolecular macrocyclic receptors in terms of their topological structure, host-guest properties and synthesis yield. At the same time, based on their easy functional modification, they have successfully realized the research on their host-guest recognition, adsorption of radioactive pollutants and gas color change behavior of volatile organic gases.

[0007] The object of the present invention is to provide a hetero[4]arene macrocyclic compound.

[0008] A hetero[4]arene macrocyclic compound having the following general formula I:

[0009]

[0010] Another object of the present invention is to provide a method for preparing the above-mentioned hetero[4]arene macrocyclic compound. The present invention provides a method for preparing a hetero[4]arene precursor using a sodium hydroxide methanol solution as a reaction solvent, and a high-yield and high-purity intermediate product can be obtained without column chromatography. Compared with other hybrid macrocyclic syntheses, the synthesis method of the present invention for hetero[4]arene has the advantages of high yield and high catalytic efficiency. At the same time, the synthesis methods of step one and step two have the characteristics of simple operation, easy availability of raw materials and reagents, mild conditions, few reaction steps, simple post-treatment, easy separation and purification of products, high yield, etc., and are expected to achieve commercial industrialization.

[0011] A method for preparing a hetero[4]arene macrocyclic compound, comprising the following steps:

[0012] Step 1: Under nitrogen protection, ethyl bromide and 2,6-dihydroxynaphthalene in a molar ratio of 10:1 are placed in a saturated sodium hydroxide methanol solution, and stirred at 60-65° C. for reaction; after the reaction is completed, the mixture is cooled to room temperature, filtered, washed, and dried to obtain an intermediate product;

[0013] Step 2: The intermediate product, 1,3-dimethoxybenzene and polyformaldehyde in a molar ratio of 1:1:2 are dissolved in chloroform, trifluoroacetic acid is added to catalyze the reaction during stirring at room temperature, and then heated to 60°C with stirring. After the reaction is complete and cooled to room temperature, a saturated sodium bicarbonate solution is added to quench the reaction. After separation, the hetero[4]aromatic macrocyclic compound is obtained by column chromatography.

[0014] Preferably, the step 1: putting ethyl bromide and 2,6-dihydroxynaphthalene in a molar ratio of 10:1 into a round-bottom flask, preparing a saturated sodium hydroxide methanol solution, and slowly pouring the sodium hydroxide methanol solution into the round-bottom flask after the temperature of the sodium hydroxide methanol solution drops, the reaction process requires nitrogen gas protection, heating to 60-65° C. and stirring the reaction; after the reaction is completed, cooling to room temperature, filtering out excess liquid, and then rinsing with methanol solvent 2-3 times, placing in a vacuum drying oven and heating to 40-50° C. to obtain an intermediate product after drying.

[0015] Preferably, in step 2, the column chromatography eluent is petroleum ether or dichloromethane.

[0016] Preferably, the hetero[4]arene macrocyclic compound obtained in step 2 is activated by removing solvent molecules by heating.

[0017] Preferably, the activation temperature is not less than 120° C., and the activation time is not less than 9 hours.

[0018] Another object of the present invention is to provide the use of the above hetero[4]arene macrocyclic compound.

[0019] The hetero[4]arene macrocyclic compound is used as a host-guest recognition compound.

[0020] Furthermore, the hetero[4]arene macrocyclic compound can recognize silver ions.

[0021] The beneficial effects of the present invention are as follows: the trifluoroacetic acid catalytic system of the present invention is easy to operate, has mild and rapid reaction conditions, and has a high conversion rate. The hetero[4]arene synthesized by the present invention has potential application prospects in the purification of petrochemical raw materials, etc. The hetero[4]arene synthesized by the present invention can efficiently complex silver ions, thereby achieving the purpose of identification. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is the H-NMR spectrum of the hetero[4]arene compound obtained in Example 1.

[0023] Figure 2 This is the carbon spectrum of the hetero[4]arene compound obtained in Example 1.

[0024] Figure 3 This is the mass spectrum of the hetero[4]arene compound obtained in Example 1.

[0025] Figure 4 PXRD pattern simulated from hetero[4]arene crystals.

[0026] Figure 5 This is the thermogravimetric curve of the hetero[4]arene compound obtained in Example 1.

[0027] Figure 6This is the single crystal structure of the hetero[4]arene compound obtained in Example 1.

[0028] Figure 7 This is the hydrogen spectrum of the hetero[4]arene compound obtained in Example 1 after complexing with silver hexafluorophosphate.

[0029] Figure 8 This is the hydrogen spectrum of the hetero[4]arene compound obtained in Example 1 after complexing with silver hexafluoroantimonate.

[0030] Fig. 9 This is the UV-visible absorption spectrum of the hetero[4]arene compound obtained in Example 1 after complexation with silver hexafluoroantimonate and silver hexafluorophosphate. DETAILED DESCRIPTION

[0031] The following non-limiting embodiments may enable a person skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.

[0032] The test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0033] The hetero[4]arene involved in the present invention has a reaction equation as shown below:

[0034]

[0035] The present invention relates to a method for preparing hetero[4]arene, which comprises the following steps:

[0036] The first step of the reaction: put bromoethane and 2,6-dihydroxynaphthalene in a molar ratio of 10:1 into a round-bottom flask, prepare a saturated sodium hydroxide methanol solution, and slowly pour the sodium hydroxide methanol solution into the round-bottom flask after the temperature drops. The reaction process requires nitrogen gas protection, and the mixture is heated to 60-65°C and stirred for reaction. After the reaction is completed, cool to room temperature, filter out excess liquid, rinse with methanol solvent 2-3 times, place in a vacuum drying oven, heat to 40-50°C, and then dry to obtain an intermediate product;

[0037] The second step reaction: the intermediate product, 1,3-dimethoxybenzene and polyformaldehyde in a molar ratio of 1:1:2 are dissolved in chloroform, trifluoroacetic acid is added to catalyze the reaction during stirring at room temperature, and then heated to 60°C with stirring. After the reaction is complete and cooled to room temperature, saturated sodium bicarbonate solution is added to quench the reaction. After separation, the hetero[4]aromatic hydrocarbons are obtained by column chromatography.

[0038] The column chromatography eluent may be petroleum ether and dichloromethane, but is not limited thereto.

[0039] The hetero[4]arene obtained by recrystallization can be activated by removing solvent molecules by heating. Preferably, the activation temperature is not less than 120° C. and the activation time is not less than 9 hours. The activated hetero[4]arene can be directly used for host-guest recognition, adsorption of radioactive pollutants and the study of the gas-gas color change behavior of volatile organic gases.

[0040] The key technical point of the present invention is to synthesize a hybrid macrocycle composed of different structural units, and strictly control the reaction time and temperature to prevent the production of by-products and thus reduce the yield.

[0041] Example 1

[0042] Preparation of hetero[4]arene compounds

[0043]

[0044] The first step of the reaction: put 6g of ethyl bromide and 3.6g of 2,6-dihydroxynaphthalene into a round-bottom flask, prepare 50ml of saturated sodium hydroxide methanol solution, and slowly pour the sodium hydroxide methanol solution into the round-bottom flask after the temperature drops to 25°C. The reaction process requires nitrogen gas protection, and the mixture is heated to 65°C and stirred for reaction. After the reaction is completed, cool to room temperature, filter out excess liquid, rinse with methanol solvent 2-3 times, place in a vacuum drying oven, heat to 40°C, and then dry to obtain the intermediate product;

[0045] The yield of the intermediate product in Example 1 was tested to be 95%.

[0046] The second step reaction: 2g of the intermediate product, 1g of 1,3-dimethoxybenzene and 0.6g of polyformaldehyde were dissolved in 200ml of chloroform. During stirring at room temperature, 10ml of trifluoroacetic acid was added to catalyze the reaction. The mixture was then heated to 60°C and stirred. After the reaction was complete and cooled to room temperature, 50ml of saturated sodium bicarbonate solution was added to quench the reaction. After separation, the hetero[4]aromatic hydrocarbons were obtained by column chromatography, with dichloromethane as the eluent.

[0047] The yield of hetero[4]arene product in Example 1 was tested to be 30%.

[0048] The product characterization data prepared in this example are as follows:

[0049] 1H NMR (500MHz, CD2Cl2, 293K) (ppm): 7.24 (d, J = 10Hz, 4H), 6.85 (d, J = 10Hz, 4H), 6.63 (s, 2H), 5.71 (s, 2H), 4.51 (s, 2H), 4.47(s,2H),3.99(s,12H),3.95–3.93(m,4H),3.91–3.88(m,4H),3.70(s,2H),3.66(s,2H),1.24(t,J=15Hz,12H).The 13 C NMR (400MHz, CD2Cl2, 293K) δ (ppm): 156.32, 152.75, 130.02, 128.78, 124.21, 122.72, 120.73, 116.87, 95.17, 66.53, 66.53, 56.18, 54.26, 54.04, 53.83, 53.61, 53.39, 24.11, 15.50. High resolution mass spectrometry value m / z: 755.2839, corresponding to [hetero[4]arene-H] - . Melting range: 240~241℃.

[0050] The PXRD test results are as follows Figure 4 As shown, the obtained hetero[4]arene materials have good crystallinity.

[0051] TG test results are as follows Figure 5 As shown, the obtained hetero[4]arene materials have good stability.

[0052] Single crystal structure and related parameters such as Figure 6 As shown, the obtained hetero[4]arene has a good crystal structure.

[0053] The activated hetero[4]arene macrocyclic compound and silver hexafluorophosphate were added to chloroform in equal proportions at a concentration of 5 mM and heated until dissolved. The solution changed from clear to light green. The H NMR spectrum was as follows Figure 7 As shown, it is proved that hetero[4]arene is complexed with silver hexafluorophosphate.

[0054] The activated hetero[4]arene macrocyclic compound and silver hexafluoroantimonate were added to chloroform in equal proportions at a concentration of 5 mM and heated until dissolved. The solution changed from clear to light green. The H NMR spectrum was as follows Figure 8 As shown, the addition of silver hexafluoroantimonate shields the original hydrogen of hetero[4]arene, proving that hetero[4]arene is complexed with silver hexafluorophosphate.

[0055] The activated hetero[4]arene macrocyclic compound, silver hexafluoroantimonate and silver hexafluorophosphate were added to chloroform in equal proportions at a concentration of 5 mM. The obtained UV absorption spectrum is shown in the following figure: Fig. 9 , and found an obvious charge transfer interaction at 350nm, proving that the hetero[4]arene macrocyclic compound was complexed with the silver ions in the solution.

Claims

1. A hetero[4]arene macrocyclic compound having the following general formula I:

2. The method for preparing the hetero[4]arene macrocyclic compound according to claim 1, characterized in that: The steps are as follows: Step 1: Under nitrogen protection, ethyl bromide and 2,6-dihydroxynaphthalene in a molar ratio of 10:1 are placed in a saturated sodium hydroxide methanol solution, and stirred at 60-65° C. for reaction; after the reaction is completed, the mixture is cooled to room temperature, filtered, washed, and dried to obtain an intermediate product; Step 2: The intermediate product, 1,3-dimethoxybenzene and polyformaldehyde in a molar ratio of 1:1:2 are dissolved in chloroform, trifluoroacetic acid is added to catalyze the reaction during stirring at room temperature, and then heated to 60°C with stirring. After the reaction is complete and cooled to room temperature, a saturated sodium bicarbonate solution is added to quench the reaction. After separation, the hetero[4]aromatic macrocyclic compound is obtained by column chromatography.

3. The method according to claim 2, characterized in that: The step 1: putting ethyl bromide and 2,6-dihydroxynaphthalene in a molar ratio of 10:1 into a round-bottom flask, preparing a saturated sodium hydroxide methanol solution, slowly pouring the sodium hydroxide methanol solution into the round-bottom flask after the temperature of the sodium hydroxide methanol solution decreases, the reaction process requires nitrogen gas protection, heating to 60-65° C. and stirring the reaction; after the reaction is completed, cooling to room temperature, filtering out excess liquid, and then rinsing with methanol solvent 2-3 times, placing in a vacuum drying oven and heating to 40-50° C. to obtain an intermediate product after drying.

4. The method according to claim 2, characterized in that: In the step 2, the column chromatography eluent is petroleum ether or dichloromethane.

5. The method according to claim 2, characterized in that: The hetero[4]arene macrocyclic compound obtained in step 2 is activated by removing solvent molecules through heating.

6. The method according to claim 5, characterized in that: The activation temperature is not less than 120° C. and the activation time is not less than 9 hours.

7. The use of the hetero[4]arene macrocyclic compound as claimed in claim 1 as a host-guest recognition compound, characterized in that: The hetero[4]arene macrocyclic compound recognizes silver ions.

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