Asymmetric expanded macrocyclic aromatic hydrocarbon as well as preparation method and application thereof

Abstract

The invention discloses asymmetric expanded macrocyclic aromatic hydrocarbon as well as a preparation method and application thereof, and belongs to the technical field of organic materials. The structural formula of the asymmetric expanded macrocyclic aromatic hydrocarbon is shown in the specification. The invention designs and synthesizes a novel asymmetric expanded macrocyclic molecule, which can form a two-dimensional ordered membrane material in a crystalline state through self-assembly, and can be used for catalyzing the reaction of 1, 2, 4, 5-tetracyanobenzene and methanol at normal temperature without illumination.

Description

Technical Field

[0001] This invention belongs to the field of organic materials technology, specifically relating to an asymmetric extended macrocyclic aromatic hydrocarbon, its preparation method, and its application. Background Technology

[0002] Biphenyl-extended macrocyclic aromatics (MAPs), as a class of macrocyclic molecules with rigid conjugated skeletons and internal cavities, have shown broad application potential in supramolecular chemistry, organic electronics, and functional materials in recent years. Currently, research in this field mainly focuses on the synthesis and performance exploration of symmetric biphenyl-extended MAPs. These molecules are typically constructed using symmetric precursors (such as C2 or D2 symmetric monomers) under template-assisted or cyclization reactions, forming well-structured macrocyclic systems with uniform electron distribution. These symmetric macrocyclic molecules exhibit good luminescent properties or host-guest behavior in solution and can form one-dimensional or finite-dimensional ordered assembly structures in the solid state through interactions such as π–π stacking and van der Waals forces. However, symmetric biphenyl-extended MAPs have significant limitations: due to their high structural symmetry and electronic uniformity, their self-assembly behavior in the solid state is often limited to one-dimensional chain-like structures or zero-dimensional discrete stacking, making it difficult to form higher-dimensional ordered structures. This structural limitation greatly restricts their applications in two-dimensional electron transport, surface catalysis, or two-dimensional optoelectronic materials.

[0003] Currently, there are no reports in existing technologies regarding the design, synthesis, and self-assembly of asymmetric biphenyl-derived macrocyclic aromatic hydrocarbons, and there is a particular lack of asymmetric macrocyclic systems capable of achieving two-dimensional ordered self-assembly.

[0004] In addition, 1,2,4,5-Tetracyanobenzene (TCNB) is an important raw material for the synthesis of phthalocyanines. Its reaction generally requires high temperature, light, or metal ions as templates. No reaction under mild conditions has been reported. Summary of the Invention

[0005] The purpose of this invention is to provide a biphenyl-extended macrocyclic aromatic hydrocarbon with an asymmetric electronic structure and geometry, which can achieve efficient and ordered two-dimensional self-assembly in the solid state, thereby providing a new molecular platform for constructing two-dimensional organic functional materials.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: An asymmetric extended macrocyclic aromatic hydrocarbon has the following structural formula: .

[0007] The above-mentioned method for preparing asymmetric extended macrocyclic aromatic hydrocarbons includes the following steps: Step 1: Anhydrous potassium carbonate is added to an acetonitrile solution of hydroquinone and bromopentane to react, bromopentane is added again to react, and then methyl chloroacetate is added to continue the reaction to obtain methyl 2-(4-pentoxyphenoxy)acetate. The molar ratio of hydroquinone to bromopentane is 1:1, and the molar ratio of hydroquinone to methyl chloroacetate is 2:1. The reaction temperature is 80℃; Step 2: Methyl 2-(4-pentoxyphenoxy)acetate and AlCl3 are dissolved in dichloromethane, and a dichloromethane solution of biphenyl dichlorobenzyl is added dropwise to react and obtain methyl 2,2'-[biphenyl-4,4'-diylbis(methylene)bis(4-pentoxy-1,3-phenyleneoxy)]diacetate; The molar ratio of methyl 2-(4-pentoxyphenoxy)acetate to biphenyl dichlorobenzyl is 10:1; Step 3: Dissolve methyl 2,2'-[biphenyl-4,4'-dimethylbis(methylene)bis(4-pentoxy-1,3-phenyleneoxy)]diacetate and paraformaldehyde in dichloromethane, add boron trifluoride diethyl ether dropwise, observe that the solution turns deep blue, observe TLC, the starting material spot completely disappears, quenching, to obtain asymmetric extended macrocyclic aromatic hydrocarbons; The mass ratio of methyl 2,2'-[biphenyl-4,4'-dimethylbis(methylene)bis(4-pentoxy-1,3-phenyleneoxy)] diacetate to paraformaldehyde is 1:0.06.

[0008] A crystalline two-dimensional thin film material is prepared from the above-mentioned asymmetric extended macrocyclic aromatic hydrocarbon. The preparation process is as follows: the asymmetric extended macrocyclic aromatic hydrocarbon is dissolved in dichloromethane, and then petroleum ether is added. During the addition process, the liquid-liquid interface between dichloromethane and petroleum ether is ensured to be clear. The mixture is then sealed and allowed to stand to obtain a single crystal. The single crystal is dispersed in petroleum ether and ultrasonically treated to obtain AP6-1 crystalline two-dimensional thin film material.

[0009] Furthermore, the volume ratio of dichloromethane to petroleum ether used in the single crystal preparation process is 1:1.

[0010] The aforementioned crystalline two-dimensional thin film material was used as a catalyst to catalyze the reaction of 1,2,4,5-tetracyanobenzene and methanol to prepare 1,1-dimethoxy-3-amino-5,6-dicyano-1H-isoindole.

[0011] This invention designs and synthesizes a novel asymmetric extended macrocyclic molecule that can self-assemble into a two-dimensional ordered membrane material in a crystalline state, which can be used to catalyze the addition reaction of 1,2,4,5-tetracyanobenzene (TCNB) and methanol at room temperature without light irradiation. Attached Figure Description

[0012] Figure 1 To analyze the 1H NMR spectrum of the asymmetric extended macrocyclic AP6-1.

[0013] Figure 2 Crystal structure diagram of the asymmetric extended macrocyclic AP6-1.

[0014] Figure 3 This is a two-dimensional oblique packing diagram of AP6-1 single crystal.

[0015] Figure 4 This is an electron microscope image of a two-dimensional thin film formed by the self-assembly of AP6-1.

[0016] Figure 5 shows the crystal structure of 1,1-dimethoxy-3-amino-5,6-dicyano-1H-isoindole, the product of the reaction of 1,2,4,5-tetracyanobenzene and methanol. Detailed Implementation

[0017] The preferred embodiments of the present invention will now be described in detail with reference to specific examples. It should be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the invention. Those skilled in the art can make various modifications and substitutions to the present invention without departing from its spirit and essence.

[0018] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0019] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0020] Example 1 The preparation method for the novel asymmetric extended macrocyclic ring is shown in the following formula: .

[0021] Synthesis of B-1: Anhydrous potassium carbonate (13.8 g, 0.1 mol) was added to a solution of hydroquinone (11 g, 0.4 mol) and bromopentane (7.5 g, 0.2 mol) in acetonitrile (130 mL). The mixture was stirred at 80 °C for 12 h, followed by the addition of bromopentane (7.5 g, 0.2 mol) and a further reaction time of 12 h. Then, methyl chloroacetate (20.8 g, 0.2 mol) was added to the reaction mixture, and the reaction was continued for 24 h. After the reaction was complete, the mixture was filtered, washed twice with dichloromethane, and then washed twice with NaOH solution (5 g / L). The solution was separated, dried over anhydrous sodium sulfate, concentrated, and finally purified by column chromatography to obtain a white solid product B-1 (11 g, 0.045 mol), with a yield of 43.6%. 1HNMR (400 MHz, Chloroform-d) δ 6.78 – 6.71 (m,4H), 4.49 (s, 2H), 3.80 (t, J = 6.6 Hz, 2H), 3.70 (s, 3H), 1.72 – 1.62 (m,2H), 1.38 – 1.25 (m, 4H), 0.84 (t, J = 6.9 Hz, 3H).

[0022] Synthesis of D-1: Compound B-1 (12.5 g, 0.05 mol) was placed in a 500 mL round-bottom flask and dissolved in 150 mL of dichloromethane. Then, AlCl3 (1 g) was weighed and added to the flask, followed by biphenyl dichlorobenzyl (1.25 g, 0.005 mol) in 20 mL of dichloromethane until completely dissolved in a beaker. This solution was then slowly added dropwise through a constant-pressure dropping funnel to the flask (1 h). The reaction was allowed to proceed for 24 h. After the reaction was complete, a large amount of deionized water was added to a 500 mL beaker, and the resulting solution was added to the beaker to quench the reaction. The mixture was then separated using a separatory funnel. The organic phase was washed twice with water and twice with dichloromethane. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated to obtain a crude sample. The crude sample was then purified by column chromatography to obtain the yellow product D-1 (1.52 g, 1 mmol), with a yield of 43.7%. 1 HNMR(400 MHz, Chloroform-d)δ 7.50 – 7.44 (m, 4H), 7.30 (d, J = 8.0 Hz, 4H), 6.71 (d, J = 9.7 Hz, 6H), 4.56 (s, 4H), 4.04 (s, 4H), 3.85 (s, 4H), 3.78 (s, 6H), 1.77 – 1.68 (m, 4H), 1.37 (tt, J = 4.9, 1.4 Hz, 8H), 0.91 (t, J = 6.9 Hz, 6H).

[0023] Synthesis of AP6-1: Compound D-1 (1 g, 0.7 mmol) was placed in a 500 mL round-bottom flask and dissolved in 100 mL of dichloromethane. Then, 0.06 g of paraformaldehyde was weighed and added to the round-bottom flask, followed by the slow addition of 1.5 mL of boron trifluoride ether. The solution turned dark blue. TLC observation showed that the starting spot completely disappeared. The solution was quenched with saturated sodium bicarbonate, separated, and the organic phase was washed twice with dichloromethane and dried with anhydrous sodium sulfate. The solution was filtered and concentrated to obtain a crude sample. The product was purified by column chromatography to obtain a white solid product AP6-1 (300 mg, 0.2 mmol), with a yield of 30.9%. 1 HNMR(400 MHz, Chloroform-d) δ 7.36 (d, J = 8.0 Hz, 8H), 7.23 (d, J = 8.1 Hz, 8H), 6.80 (s, 4H), 6.68 (s, 4H), 4.46 (s, 8H), 4.00 (s, 8H), 3.87 (dd, J = 12.9, 6.3 Hz, 12H), 3.68 (s, 12H), 1.80 (p, J = 6.8 Hz, 8H), 1.50-1.35 (m, 16H), 0.92 (t, J = 7.1 Hz, 12H).

[0024] like Figure 1 As shown, the 1H NMR spectrum clearly shows 16 (8+8) hydrogen atoms on the biphenyl ring, 8 (4+4) hydrogen atoms on the asymmetric monomer benzene ring, 12 hydrogen atoms on the bridging carbon, 44 hydrogen atoms (12+8+16+8) on the alkyl chain, and 20 hydrogen atoms (12+8) on the ester group. No obvious impurity peaks were observed.

[0025] Example 2 Preparation of AP6-1 crystalline two-dimensional materials Single crystals of AP6-1 were obtained by solvent diffusion of petroleum ether into a dichloromethane solution (petroleum ether: dichloromethane = 1:1). Specifically, 10 mg of AP6-1 was weighed, dissolved in 2 mL of dichloromethane, and filtered. The filtrate was placed in a 5 mL transparent sample bottle, and 2 mL of petroleum ether was slowly added along the bottle wall, ensuring a clear interface between the dichloromethane and petroleum ether. After adding the petroleum ether, the bottle was capped and allowed to stand for two days to obtain AP6-1 single crystals. The AP6-1 single crystals were dispersed in petroleum ether and sonicated for 10 minutes to obtain AP6-1 crystalline two-dimensional thin film material.

[0026] X-ray single-crystal diffraction tests were performed on AP6-1 single crystals. The specific test parameters were: XtaLAB Synergy R, DWsystem, HyPix diffractometer, temperature 150.00(10)K, and structural analysis was performed using Olex2 and SHELXT. The X-ray single-crystal diffraction test results are shown in Table 1.

[0027] Table 1 AP6-1 Single Crystal Data Sheet (CCDC No.: 2481111)

[0028] A schematic diagram of the single-crystal molecular packing of AP6-1 is shown below. Figure 3 As shown.

[0029] like Figure 4 As shown, in the two-dimensional thin film formed by the self-assembly of AP6-1, molecules can spontaneously aggregate, recognize, and form a stable layered structure through weak interactions without the need for external forces.

[0030] Example 3 AP6-1 crystalline two-dimensional material catalyzes the reaction of 1,2,4,5-tetracyanobenzene and methanol. 10 mL of dichloromethane and 10 mL of methanol were added to a 50 mL round-bottom flask, followed by the addition of 1,2,4,5-tetracyanobenzene (89 mg) and AP6-1 (10 mg) as catalysts. The mixture was stirred for one minute to ensure complete homogeneity, and then allowed to stand for two days. TLC observation showed the disappearance of the raw material spots, resulting in 120 mg of pale yellow crystals. X-ray single-crystal diffraction was performed on the generated single crystal. The specific test parameters were: XtaLAB Synergy R, DW system, HyPix diffractometer, temperature 150.00 (10) K, and structural analysis was performed using Olex2 and SHELXT. The X-ray single-crystal diffraction results are as follows: Figure 5 As shown in Table 2.

[0031] Table 2 Crystal data and structure refinement for 1,1-dimethoxy-3-amino-5,6-dicyano-1H-isoindole

[0032] This invention designs and synthesizes a novel asymmetric extended macrocyclic molecule that can self-assemble into a two-dimensional ordered membrane material in a crystalline state for use in the addition reaction of 1,2,4,5-tetracyanobenzene and methanol at room temperature without light irradiation.

Claims

1. An asymmetric extended macrocyclic aromatic hydrocarbon, the structural formula of which is shown below: 。 2. The method for preparing asymmetric extended macrocyclic aromatic hydrocarbons according to claim 1, characterized in that, Includes the following steps: Step 1: Anhydrous potassium carbonate is added to an acetonitrile solution of hydroquinone and bromopentane to react, bromopentane is added again to react, and then methyl chloroacetate is added to continue the reaction to obtain methyl 2-(4-pentoxyphenoxy)acetate. Step 2: Methyl 2-(4-pentoxyphenoxy)acetate and AlCl3 are dissolved in dichloromethane, and a dichloromethane solution of biphenyl dichlorobenzyl is added dropwise to react and obtain methyl 2,2'-[biphenyl-4,4'-diylbis(methylene)bis(4-pentoxy-1,3-phenyleneoxy)]diacetate; Step 3: Dissolve methyl 2,2'-[biphenyl-4,4'-dimethylbis(methylene)bis(4-pentoxy-1,3-phenyleneoxy)]diacetate and paraformaldehyde in dichloromethane, add boron trifluoride diethyl ether dropwise, observe that the solution turns dark blue, observe TLC, the starting material spot completely disappears, indicating quenching, and obtain asymmetric extended macrocyclic aromatic hydrocarbons.

3. The preparation method according to claim 2, characterized in that, In step 1, the molar ratio of hydroquinone to bromopentane is 1:1, and the molar ratio of hydroquinone to methyl chloroacetate is 2:

1.

4. The preparation method according to claim 2, characterized in that, In step 1, the reaction temperature is 80℃.

5. The preparation method according to claim 2, characterized in that, In step 2, the molar ratio of methyl 2-(4-pentoxyphenoxy)acetate to biphenyl dichlorobenzyl is 10:

1.

6. The preparation method according to claim 2, characterized in that, In step 3, the mass ratio of methyl 2,2'-[biphenyl-4,4'-dimethylbis(methylene)bis(4-pentoxy-1,3-phenyleneoxy)] diacetate to paraformaldehyde is 1:0.

06.

7. A crystalline two-dimensional thin film material, characterized in that, The asymmetric extended macrocyclic aromatic hydrocarbon described in claim 1 is prepared by dissolving the asymmetric extended macrocyclic aromatic hydrocarbon described in claim 1 in dichloromethane, then adding petroleum ether, ensuring a clear liquid-liquid interface between dichloromethane and petroleum ether during the addition process, sealing and allowing it to stand to obtain a single crystal; dispersing the single crystal in petroleum ether and sonicating it to obtain AP6-1 crystalline two-dimensional thin film material.

8. The crystalline two-dimensional thin film material according to claim 7, characterized in that, The volume ratio of dichloromethane to petroleum ether used in the preparation of single crystals is 1:

1.

9. The crystalline two-dimensional thin film material of claim 8 is used as a catalyst for the catalytic reaction of 1,2,4,5-tetracyanobenzene and methanol to prepare 1,1-dimethoxy-3-amino-5,6-dicyano-1H-isoindole.

Images