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CN-122010738-A - Asymmetric expansion macrocyclic aromatic hydrocarbon and preparation method and application thereof

CN122010738ACN 122010738 ACN122010738 ACN 122010738ACN-122010738-A

Abstract

The invention discloses asymmetric expansion macrocyclic arene and a preparation method and application thereof, and belongs to the technical field of organic materials. The structural formula of the asymmetric expanded macrocyclic arene is shown as follows: . The invention designs and synthesizes a novel asymmetric expansion 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 under non-illumination.

Inventors

  • YAO YONG
  • LIANG XUFENG
  • WANG YANG
  • ZHANG JIANXIA
  • DENG CHUNLIN

Assignees

  • 南通大学

Dates

Publication Date
20260512
Application Date
20251212

Claims (9)

  1. 1. An asymmetric expansion macrocyclic arene has a structural formula shown as follows: 。
  2. 2. the method for preparing the asymmetric extended macrocyclic arene according to claim 1, comprising the following steps: Step 1, adding anhydrous potassium carbonate into acetonitrile solution of hydroquinone and bromopentane for reaction, adding bromopentane again for reaction, and then adding methyl chloroacetate for continuous reaction to obtain 2- (4-pentoxyphenoxy) methyl acetate; Step 2, dissolving methyl 2- (4-pentoxyphenoxy) acetate and AlCl 3 in dichloromethane, dropwise adding dichloromethane solution of biphenyl dichlorobenzyl for reaction to obtain methyl 2,2'- [ biphenyl-4, 4' -diylbis (methylene) bis (4-pentoxy-1, 3-phenylene oxy) ] diacetate; step 3, dissolving methyl 2,2'- [ biphenyl-4, 4' -diylbis (methylene) bis (4-pentyloxy-1, 3-phenylene oxy) ] diacetate and paraformaldehyde in methylene dichloride, dropwise adding boron trifluoride diethyl ether, observing the solution to turn deep blue, and quenching to obtain the asymmetric expanded macrocyclic arene after the point plate is observed and the raw material point completely disappears.
  3. 3. The process according to claim 2, wherein 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. 4. The process according to claim 2, wherein in step 1, the reaction temperature is 80 ℃.
  5. 5. The process according to claim 2, wherein in step 2, the molar ratio of methyl 2- (4-pentoxyphenoxy) acetate to biphenyl dichlorobenzene is 10:1.
  6. 6. The method according to claim 2, wherein in step 3, the mass ratio of methyl 2,2'- [ biphenyl-4, 4' -diylbis (methylene) bis (4-pentoxy-1, 3-phenylene oxy) ] diacetate to paraformaldehyde is 1:0.06.
  7. 7. The crystalline two-dimensional film material is characterized by being prepared from the asymmetric expanded macrocyclic arene according to claim 1, and the preparation process comprises the steps of dissolving the asymmetric expanded macrocyclic arene according to claim 1 in dichloromethane, then adding petroleum ether, ensuring clear interface between the dichloromethane and the petroleum ether liquid in the adding process, sealing and standing to obtain single crystals, dispersing the single crystals in the petroleum ether, and carrying out ultrasonic treatment to obtain the AP6-1 crystalline two-dimensional film material.
  8. 8. The crystalline two-dimensional thin film material of claim 7, wherein the volume ratio of dichloromethane to petroleum ether used in the preparation of the single crystal is 1:1.
  9. 9. The crystalline two-dimensional thin film material of claim 8 used as a catalyst for catalyzing the reaction of 1,2,4, 5-tetracyanobenzene with methanol to prepare 1, 1-dimethoxy-3-amino-5, 6-dicyano-1H-isoindole.

Description

Asymmetric expansion macrocyclic aromatic hydrocarbon and preparation method and application thereof Technical Field The invention belongs to the technical field of organic materials, and particularly relates to asymmetric expansion macrocyclic aromatic hydrocarbon, and a preparation method and application thereof. Background The biphenyl expanded macrocyclic arene has wide application potential in the fields of supermolecular chemistry, organic electronics and functional materials in recent years as a class of macrocyclic molecules with rigid conjugated skeletons and internal cavities. At present, the research in the field mainly focuses on the synthesis and performance exploration of symmetrical biphenyl extended macrocyclic aromatic hydrocarbon. Such molecules are typically built by a symmetry reaction precursor (e.g., a C 2 or D 2 symmetry monomer) under a template-assisted or cyclization reaction to form a structurally ordered, electron-distributed macrocyclic system. The symmetrical macrocyclic molecules show good luminescence characteristics or host-guest behavior in solution, and can form one-dimensional or limited-dimensional ordered assembly structures through pi-pi stacking, van der Waals force and other interactions in the solid state. However, symmetrical biphenyl extended macrocyclic arenes have obvious limitations in that their self-assembly behavior in the solid state is often limited to one-dimensional chain or zero-dimensional discrete stacks due to their high symmetry and electronic uniformity of structure, and it is difficult to form higher-dimensional ordered structures. This structural limitation has led to a great restriction in its application in the fields of two-dimensional electron transport, surface catalysis or two-dimensional photoelectric materials. At present, reports about design, synthesis and self-assembly research of asymmetric biphenyl expanded macrocyclic aromatic hydrocarbon are not yet seen in the prior art, and an asymmetric macrocyclic system capable of realizing two-dimensional ordered self-assembly is especially lacking. In addition, 1,2,4, 5-Tetracyanobenzene (TCNB) is an important raw material for synthesizing phthalocyanine, and its reaction generally requires high temperature, light or metal ions as templates, and no reaction has been reported under mild conditions. Disclosure of Invention The invention aims to provide biphenyl expansion macrocyclic arene with an asymmetric electronic structure and a geometric configuration, which can realize efficient and ordered two-dimensional self-assembly in a solid state, thereby providing a novel molecular platform for constructing a two-dimensional organic functional material. In order to achieve the above purpose, the present invention adopts the following technical scheme: an asymmetric expansion macrocyclic arene has a structural formula shown as follows: 。 The preparation method of the asymmetric expansion macrocyclic arene comprises the following steps: Step 1, adding anhydrous potassium carbonate into acetonitrile solution of hydroquinone and bromopentane for reaction, adding bromopentane again for reaction, and then adding methyl chloroacetate for continuous reaction to obtain 2- (4-pentoxyphenoxy) methyl acetate; the mol ratio of hydroquinone to bromopentane is 1:1, and the mol ratio of hydroquinone to methyl chloroacetate is 2:1; The reaction temperature is 80 ℃; Step 2, dissolving methyl 2- (4-pentoxyphenoxy) acetate and AlCl 3 in dichloromethane, dropwise adding dichloromethane solution of biphenyl dichlorobenzyl for reaction to obtain methyl 2,2'- [ biphenyl-4, 4' -diylbis (methylene) bis (4-pentoxy-1, 3-phenylene oxy) ] diacetate; The molar ratio of the methyl 2- (4-pentoxyphenoxy) acetate to the biphenyl dichlorobenzyl is 10:1; Step 3, dissolving methyl 2,2'- [ biphenyl-4, 4' -diylbis (methylene) bis (4-pentoxy-1, 3-phenylene oxy) ] diacetate and paraformaldehyde in methylene dichloride, dropwise adding boron trifluoride diethyl ether, observing a dot plate, completely disappearing a raw material dot, and quenching to obtain asymmetric expanded macrocyclic arene; The mass ratio of methyl 2,2'- [ biphenyl-4, 4' -diylbis (methylene) bis (4-pentoxy-1, 3-phenylene oxy) ] diacetate to paraformaldehyde was 1:0.06. The crystalline two-dimensional film material is prepared by dissolving the asymmetric expanded macrocyclic aromatic hydrocarbon in methylene dichloride, then adding petroleum ether, ensuring clear liquid-liquid interface between the methylene dichloride and the petroleum ether in the adding process, sealing and standing to obtain single crystals, dispersing the single crystals in the petroleum ether, and carrying out ultrasonic treatment to obtain the AP6-1 crystalline two-dimensional film material. Further, the volume ratio of dichloromethane to petroleum ether adopted in the process of preparing the single crystal is 1:1. The crystalline two-dimensional film material is used as a catalyst for catal