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CN-121974792-A - Supermolecule macrocyclic arene constructed based on naphthalene ring and diphenyl ketone, and synthetic method and application thereof

CN121974792ACN 121974792 ACN121974792 ACN 121974792ACN-121974792-A

Abstract

The invention discloses a supermolecule macrocyclic arene constructed based on naphthalene rings and diphenyl ketone, and a synthesis method and application thereof, belonging to the technical field of supermolecule chemistry. The supermolecule macrocyclic arene takes naphthalene ring and diphenyl ketone as construction units, forms a central symmetrical structure through methylene bridge connection, has the characteristics of a hexagonal electron-deficient cavity and a non-covalent molecular pipeline, and comprises two steps of Friedel-Crafts acyl synthesis intermediate and cyclization condensation synthesis target product, and has the advantages of mild reaction conditions, simple operation and high cyclization yield. The invention also discloses a red-red charge transfer composite material formed by the macrocyclic arene and the 1,2,4, 5-tetracyanobenzene, the composite material has specific gasochromic response to benzene vapor, the color of the composite material is changed from red to orange-brown after benzene vapor is adsorbed, no obvious response to other benzene pollutants such as toluene, xylene and the like exists, and the composite material can be used for rapid and visual detection of the benzene vapor. The invention has important application value in the fields of supermolecule sensing and environmental monitoring.

Inventors

  • SHI BINGBING
  • Peng Pengjia
  • WEI TAIBAO

Assignees

  • 西北师范大学

Dates

Publication Date
20260505
Application Date
20260128

Claims (10)

  1. 1. A supermolecule macrocyclic arene constructed based on naphthalene rings and benzene has the structural formula: 。
  2. 2. the supermolecular macrocyclic arene according to claim 1, wherein the macrocyclic arene has naphthalene rings and benzophenone as building blocks, and is connected via methylene bridges to form nano-sized electron-deficient cavities having a centrosymmetric structure, the cavities being hexagonal-like, the long axis is 13.53A, the short axis is 10.09A, and all units connected by methylene bridges are staggered and not on the same plane, and C-H.pi acting force exists between methyl groups and naphthalene rings of adjacent units, so that a non-covalent molecular pipeline can be formed.
  3. 3. The method for synthesizing the supermolecular macrocyclic arene according to claim 1 or 2, comprising the following steps: a. In the presence of a catalyst, performing Friedel-Crafts acylation reaction on alkoxy naphthalene and terephthaloyl chloride in an organic solvent to obtain an intermediate fragment; the structural formula of the intermediate fragment is as follows: ; b. and c, performing cyclization condensation reaction on the intermediate fragment obtained in the step a and paraformaldehyde in a Lewis acid catalyst and an organic solvent to obtain the supermolecule macrocyclic arene.
  4. 4. The method according to claim 3, wherein in the step a, the alkoxynaphthalene is 2, 6-dimethoxynaphthalene, the catalyst is aluminum trichloride, and the organic solvent is dichloromethane.
  5. 5. The synthetic method according to claim 3, wherein in the step a, the molar ratio of terephthaloyl chloride to alkoxynaphthalene is 1:4-1:5, the molar amount of the catalyst is 1.3-1.4 times the molar amount of terephthaloyl chloride, and the Friedel-Crafts acylation reaction is carried out at 30-50 ℃ for 5-6 hours.
  6. 6. The synthetic method according to claim 3, wherein in the step b, the Lewis acid catalyst is boron trifluoride diethyl etherate, the organic solvent is 1, 2-dichloroethane, the molar ratio of the intermediate fragment to paraformaldehyde is 1:2-1:4, the molar amount of the Lewis acid catalyst is 2 times that of the intermediate fragment, and the cyclized condensation reaction is carried out at 40-60 ℃ for 10-20min.
  7. 7. A charge transfer composite material characterized in that the supermolecular macrocyclic arene according to claim 1 or 2 is used as a host, 1,2,4, 5-tetracyanobenzene is used as a guest, and the host and the guest form a reddish host-guest complex through charge transfer.
  8. 8. Use of the composite material according to claim 7 in the detection of the gasochromic effect of benzene vapors.
  9. 9. The method according to claim 8, wherein the composite material is exposed to the gaseous environment to be measured and the color change is observed, and wherein if the color of the material changes from reddish to orange-brown, the presence of benzene vapor in the gaseous environment to be measured is indicated.
  10. 10. The use of claim 9, wherein the gaseous environment to be tested is a gaseous environment containing benzene-based contaminants including one or more of benzene, toluene, ortho-xylene, meta-xylene, para-xylene, and wherein the color change is selective to benzene.

Description

Supermolecule macrocyclic arene constructed based on naphthalene ring and diphenyl ketone, and synthetic method and application thereof Technical Field The invention belongs to the technical field of organic synthetic chemistry and supermolecular chemistry, and particularly relates to supermolecular macrocyclic arene constructed based on naphthalene rings and diphenyl ketone, a synthetic method thereof, and application of a charge transfer composite material formed by the macrocyclic arene in benzene steam detection. Background Macrocyclic aromatic compounds have long been regarded as important research objects in the field of supramolecular chemistry due to their unique molecular recognition capabilities and host-guest complexation behavior. With the continuous and deep research of related research, the compound has wide application potential in the fields of functional material construction, biomedical systems and chemical related fields. Therefore, the design and synthesis of supramolecular macrocyclic host molecules surrounding novel framework configurations and specific physicochemical properties has become an important direction in current supramolecular chemistry research. Particularly, macrocyclic aromatic hydrocarbon systems having both a large and deep space structure, tunable optical response, and unique spatial configuration have received attention in recent years. However, the construction of such macrocyclic host molecules still faces a certain technical difficulty due to limitations in terms of structural complexity and synthesis controllability. In recent years, with the rapid development of the research fields of supermolecular chemistry and organic macrocyclic aromatic hydrocarbon, in addition to the traditional calixarene and column aromatic hydrocarbon systems, various novel macrocyclic aromatic hydrocarbon main molecules with novel structures and different functional characteristics are reported successively. Naphthalene ring is used as an extended pi conjugated unit with proper space size and good optical response characteristic, and alkoxy substituted derivatives thereof gradually develop into important structural elements for constructing novel supermolecule macrocycles. The benzene in the benzene-based pollutant has obvious hazard and wide distribution, and the research and development of the high-selectivity sensing material becomes a research hot spot in the field of environmental monitoring, so that the material has irreplaceable application value in the scenes of industrial waste gas treatment, indoor air purification, water quality safety monitoring, occupational health protection and the like. But the benzene molecule has a simple structure and does not contain conjugated chromophoric or fluorescent functional groups, thereby bringing great challenges to visual qualitative and quantitative detection. At present, detection technologies such as a gas chromatography, a gas chromatography-mass spectrometry combined method, a high performance liquid chromatography and the like commonly used often depend on large-scale precise instruments, and the defects of complicated operation flow, long detection period, difficult on-site rapid deployment and the like exist, so that the actual requirements of real-time emergency monitoring cannot be met. The optical sensing technology based on optical signal response has the advantages of high response speed, simplicity and convenience in operation, excellent sensitivity, low cost, capability of realizing in-situ real-time monitoring and the like, can effectively break through the bottleneck of the traditional detection means, becomes a core research direction in the field of rapid detection of benzene pollution, and has very wide application prospect. The appearance of each new type of macrocyclic main body enriches the researches of main guest chemistry and supermolecule chemistry, however, no report on supermolecule acceptor macrocycles constructed by connecting naphthalene rings and benzophenone units through methylene bridges and the use of supermolecule acceptor macrocycles as benzene vapor selective gasochromic detection materials is yet to be seen, so that the design synthesis of macrocyclic aromatic hydrocarbons constructed based on naphthalene rings and benzophenone and the application of macrocyclic aromatic hydrocarbons still have important research values. Disclosure of Invention The invention aims to provide supermolecule macrocyclic arene constructed based on naphthalene rings and diphenyl ketone, which has a specific cavity structure and non-covalent bond molecular pipeline characteristics, and provides novel main molecules for supermolecule assembly, adsorption separation and sensing material development. The invention also aims to provide the synthesis method of the supermolecule macrocyclic arene, which has the advantages of mild reaction conditions, simple operation and high cyclization yield, and overcomes the defects of sev