| Summary: | 碩士 === 國立交通大學 === 應用化學系 === 88 === Abstract
This thesis reports three synthetic routes for the preparation of various lower-rim and upper-rim substituted calix[4]arenes. The first part of this thesis is forcussed at the synthesis of new series of upper-rim isoxazoline-substituted calix[4]arenes. In preparing these isoxazoline substituted calix[4]arenes, the number of the incorporated isoxazoline moieties was determined by factors such as reaction time, amount of triethylamine and benzohydroximinoyl chloride. It is found that shorter reaction time and less amount of triethylamine and benzohydroximinoyl chloride makes the product dominated by monoisoxazoline-substituted calix[4]arene, otherwise, diisoxazoline-substuted calix[4]arene becomes the major product.
The second part of this thesis describes the synthesis of upper-rim diazo-substituted calix[4]arene. Different kinds of alkyl halides were induced to 25,27-diallyloxy-26-benzoyloxy-28-hydroxycalix[4]arene 47 to increase the solubility and decrease the melting transition. The two lower-rim allyl moieties were rearranged to the para-position by thermal induced Claisen rearrangement reaction. However, the yield of this rearrangement reaction is unexpectedly low, resulting in the difficulty of further investigation.
The third part of this thesis focuses on the synthesis of thione-containing calix[4]arene for the attempt to increase the chelate ability. 25,26,27,28-tetrahydroxycalix[4]arene 7 was protected by using benzoyl chloride and the resulting compounds were oxidized by ClO2 to yield calix[4]quinone. This calix[4]quinone 55 was reacted with P4S10 to yield the product of 25,26,27-tribenzoyloxy-28-calix[4]dithioquinone 56.
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