Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Functionalized pillar arene derivatives and preparation method thereof

A technology for pillar aromatic hydrocarbons and derivatives, which is applied in the field of derivatives and corresponding preparations, can solve the problems that pillar aromatic hydrocarbon functionalization methods are yet to be developed, limit the application of functionalized pillar aromatic hydrocarbons, and the like, and achieves the effects of mild reaction conditions and simple synthesis.

Active Publication Date: 2021-11-05
SHANGHAI ADVANCED RES INST CHINESE ACADEMY OF SCI
View PDF3 Cites 0 Cited by
  • 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Functionalized pillar arene derivatives and preparation method thereof
  • Functionalized pillar arene derivatives and preparation method thereof
  • Functionalized pillar arene derivatives 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.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a functionalized pillar arene derivative and a preparation method thereof. The functionalized pillar arene derivative contains: an X unit, a Y unit and a Z unit, wherein the X unit is as shown in formula (I), and the Y unit is as shown in formula ( II), the Z unit is as shown in formula (III), the X unit, the six-membered ring of the Y unit and the Z unit all have two para-position substituents, and there are four unsubstituted positions; between CH 2 The groups are connected to form a ring structure, and the connection mode of each unit is that the unsubstituted position is connected to the other two adjacent units in the form of a para position; the formed ring structure is derived from the functionalized pillar arene things. The present invention expands the means of functionalization of pillar aromatics by directly connecting cyano, carboxyl, and oxime to the pillar aromatic hydrocarbon benzene ring monomer, and the connected groups can effectively change the electronic environment of the pillar aromatic hydrocarbon ring. Subject-object recognition and other fields have a wide range of applications.

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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(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
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com