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Functionalized column aromatic hydrocarbon derivative and preparation method thereof

A technology for pillar aromatics and derivatives, which is applied in the field of derivatives and corresponding preparations, and can solve the problems of undeveloped means of functionalizing pillar aromatics and limiting the application of functionalized pillar aromatics

Active Publication Date: 2019-03-01
SHANGHAI ADVANCED RES INST CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But recently, there are few reports on the synthesis of new functionalized pillararenes, especially the benzene ring monomers of directly functionalized pillararenes (functional groups are directly connected to the benzene ring monomers without ether bonds), which also limits the development of functionalized pillararenes. For further application, the functionalization means of pillar aromatics need to be developed

Method used

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  • Functionalized column aromatic hydrocarbon derivative and preparation method thereof
  • Functionalized column aromatic hydrocarbon derivative and preparation method thereof
  • Functionalized column aromatic hydrocarbon derivative and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0114] The synthetic route of embodiment 1 compound 1-2:

[0115]

[0116] (1) Synthesis of compound A-1: ​​p-xylylene dimethyl ether (1.38g, 10mmol), paraformaldehyde (300mg, 10mmol) and boron trifluoride ether (1.25ml, 10mmol) were added to 25ml of 1 , 2-dichloroethane, stirred at room temperature for 40min. The color of the reaction solution changed from cloudy white to dark green. Thin-layer chromatography (Thin-layer chromatography, TLC) board confirms that the reaction is complete, the reaction solution is washed twice with 20ml water, the organic layer is concentrated under reduced pressure to obtain a crude product, which is then dissolved in dichloromethane and mixed with silica gel powder, and separated by column chromatography to obtain Pure white solid A-1 (1 g, yield 60%). 1 H-NMR (500MHz, CDCl 3 , 298K): δ6.84(s, 10H), 3.76(s, 10H), 3.71(s, 30H). 13 C-NMR (CDCl 3 , 67.5MHz, ppm): 6150.4, 128.0, 133.6, 55.5, 29.5. ESI-HRMS (electrospray-high resolution mas...

Embodiment 2

[0129] The synthetic route of embodiment 2 compound 1-4 is as follows:

[0130]

[0131] Its preparation method can refer to I-2. Wherein, the molar equivalent ratio of step (2) A-1 to ammonium cerium nitrate is 1:4, and the reaction time is 10 min. Wherein, the molar equivalent ratio of step (3) B-2 to sodium borohydride is 1:5, and the stirring time is 10 min. Wherein, the molar equivalent ratio of step (4) C-2 to base and trifluoromethanesulfonic anhydride is 1:6:6, and the reaction time is 10 h. Wherein, the molar equivalent ratio of step (5) D-2, zinc cyanide and catalyst is 1:4:0.2. The binding constant of the target compound I-3 with 1,6-adiponitrile (deuterated chloroform, 25°C) is 2.1±0.3M after nuclear magnetic titration test -1 .

[0132] see Figure 5-8 , Figure 5 for the target compound I-3 1 H-NMR spectrum; Figure 6 for the target compound I-3 13 C-NMR spectrum; Figure 7 For the target compound I-4 1 H-NMR spectrum; Figure 8 For the target comp...

Embodiment 3

[0133] The synthetic route of embodiment 3 compound 1-6 is as follows:

[0134]

[0135] Its preparation method can refer to I-2. Wherein, the molar equivalent ratio of step (2) A-1 to ammonium cerium nitrate is 1:6, and the reaction time is 20 minutes. Wherein, the molar equivalent ratio of step (3) B-3 to sodium borohydride is 1:7.5, and the stirring time is 15 min. Wherein, the molar equivalent ratio of step (4) C-3 to base and trifluoromethanesulfonic anhydride is 1:9:9, and the reaction time is 10 h. Wherein, the molar equivalent ratio of step (5) D-3, zinc cyanide and catalyst is 1:6:0.3.

[0136] see Figure 9-12 ,in Figure 9 For the target compound I-5 1 H-NMR spectrum; Figure 10 for 3 target compounds I-5 13 C-NMR spectrum; Figure 11 for the target compound I-6 1 H-NMR spectrum; Figure 12 It is the high resolution mass spectrum of the target compound I-6.

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Abstract

The invention discloses a functionalized column aromatic hydrocarbon derivative and a preparation method thereof. The functionalized column aromatic hydrocarbon derivative comprises an X unit, a Y unit and a Z unit, wherein the X unit is shown in a formula (I), the Y unit is shown in a formula (II), the Z unit is shown in a formula (III), and the six-membered rings of the X unit, the Y unit and the Z unit all have two para-position substituents and four unsubstituted positions; the formulas are as shown in the specification, each unit is connected through CH2 groups to form a ring-shaped structure, and each unit is connected with the other two adjacent units in a para-position manner at an unsubstituted position; and the formed ring-shaped structure is the functionalized column aromatic hydrocarbon derivative. Cyano groups, carboxyl groups and oxime are directly connected to the benzene ring monomer of the column aromatic hydrocarbon, so that the method for functionalizing the column aromatic hydrocarbon is expanded; and the connected groups can effectively change the electronic environment of the column aromatic hydrocarbon rings, so that the functionalized column aromatic hydrocarbon derivative has wide application in the fields of supramolecular host-guest identification and the like.

Description

technical field [0001] The invention belongs to the technical field of pylarene derivatives, and specifically relates to cyanylation, carboxylation and oximation derivatives of pylarene and a corresponding preparation method. Background technique [0002] Supramolecular chemistry is an emerging interdisciplinary subject that studies complex, ordered molecular aggregates with specific functions formed through non-covalent interactions between molecules. Macrocyclic hosts are one of the important foundations for the construction of supramolecular chemistry and one of the main driving forces for the development of supramolecular chemistry. Crown ethers, cyclodextrins, and calixarenes belong to the first, second, and third generation macrocyclic molecules, respectively. In 2008, pillararenes, as a new generation of macrocyclic molecules, were reported to be synthesized for the first time. Pillararenes are a kind of cyclic oligomers formed by linking hydroquinone or hydroquinon...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C255/54C07C65/24C07C255/52C07C63/48C07C251/46C07C41/28C07C43/20C07C50/36C07C46/00C07C43/23C07C41/26C07C309/66C07C303/28C07C253/16C07C51/08C07C249/08
CPCC07C41/26C07C41/28C07C43/20C07C43/23C07C46/00C07C50/36C07C51/08C07C63/48C07C65/24C07C249/08C07C251/46C07C253/16C07C255/52C07C255/54C07C303/28C07C309/66C07C2603/92
Inventor 文珂汪果谢长东王焯李昆昂胡维波陈涛
Owner SHANGHAI ADVANCED RES INST CHINESE ACADEMY OF SCI
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