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

被引：77
|
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
收藏
页码：1166 / 1172
页数：7
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