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Aminolysis reaction of calix[4]arene esters and crystal structures and conformational behaviors of calix[4]arene amides

โœ Scribed by Wu Yong; Liu Hui-Biao; Hu Jun; Liu Yong-Jiang; Duan Chun-Ying; Xu Zheng


Publisher
John Wiley and Sons
Year
2010
Tongue
English
Weight
635 KB
Volume
18
Category
Article
ISSN
0256-7660

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โœฆ Synopsis


Abstract

We first make use of aminolysis of calix[4]arene esters to synthesize calix[4]arene amides. When the two ethyl esters of the calix[4]arene esters are aminolysized, the 1, 3โ€amide derivative is formed selectively. The crystal structures of the calixโ€[4] arene with two butyl amide (3b) and four butyl amide moieties (4b) were determined. The intermolecular hydrogen bonds make 4b form twoโ€dimensional net work insolid state. The ^1^H NMR spectra prove mat 3b is of a pinched cone conformation, while 4b and tetraheptylamideโ€calix[4]arene (6b) take fast interconversion between two C~2r~ isomers in solution and appear an apparent cone conformation at room temperature. As decreasing temperature, the interconversion rate decreases gradually and, finally, the interconversion process is frozen at T~c~ = โˆ’10ยฐC, which makes both conformations of 4b and 6b the pinched cone structures. The hydrogen bond improves the interconversion barrier, and the large different values of the potential barrier between 6b and 4b (or 6b) may be of forming different hydrogen bonds.


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