Acid-base properties of sulfur-bridged calix[4]arenes

被引：78

作者：

Matsumiya, H ^{[1
]}

Terazono, Y ^{[1
]}

Iki, N ^{[1
]}

Miyano, S ^{[1
]}

机构：

[1] Tohoku Univ, Grad Sch Engn, Dept Biomol Engn, Aoba Ku, Sendai, Miyagi 9808579, Japan

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 2002年 / 06期

关键词：

D O I：

10.1039/b200228k

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The acid-base properties of sulfur-bridged calixarenes, thiacalix[4]arenetetrasulfonate (4) and its sulfonyl analogue (5), have been investigated via potentio- and spectrophoto-metric studies, comparing them with the conventional methylene-bridged calix[ 4] arenetetrasulfonate (3). The titration curves revealed the acidity of the phenolic OH groups in the calix[4]arenes 3-5 to be in the order: 3 < 4 << 5. In particular, the oxidation of the bridging sulfur to sulfone strongly enhanced the acidity of the sulfur-bridged calix[ 4] arene; the pK(a,n) values (n = 2-4) of the sulfone-bridged 5 were lower by 7 pK units than those of the sulfide-bridged 4. The effects of the linkage groups on the acidity of the calix[4]arenes are discussed from the structural and electronic viewpoints, such as the macrocyclic ring size, the hydrogen bonding manner, and the resonance of the linkage moiety.

引用

页码：1166 / 1172

页数：7

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