Abstract
Side arm modifications of hexahomotriazacalix[3]arene (1) were achieved by simple synthetic methods. Compound5 has picolyl side arms and liquid-liquid extraction experiments showed that the alkali cation affinity of5 is much stronger than that of1. A chiral group was also introduced into the azacalixarene structure. Calix[4]arene was converted into dihomoazacalix[4]arene (2) in 8% yield. Clathrate formation of2 with various solvents is described. MM3 calculations were carried out onp-substituted analogs of2. The ‘self-filled’ structure, in which the benzyl side arm is placed in its cavity, is the most stable structure when thep-positions of the aromatic rings carry small substituents. Strong hydrogen bonds between nitrogen and phenolic hydroxyl groups in dihomoazacalix[4]arene (2) were observed at low temperatures. The1H-NMR signals of phenolic hydroxyl groups appeared as six singlets in the range of 9.8∼17.1 ppm at −70°C.
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MM3 calculations were carried out with a MM3 ('92) program in its ANCHOR II implementation. ANCHOR II is a molecular design support system for SUN computers from Fujitsu Limited. Trade Mark of Fujitsu Limited and Kureha Chemical Company, 1992. In these calculations, the memory size of the hardware was limited, thus, molecules larger thanp-diisopropyldihomoazacalix[4]arene were not considered for the model.
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This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.
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Takemura, H., Shinmyozu, T., Miura, H. et al. Synthesis and properties ofN-substituted azacalix[n]arenes. J Incl Phenom Macrocycl Chem 19, 193–206 (1994). https://doi.org/10.1007/BF00708982
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DOI: https://doi.org/10.1007/BF00708982