上緣含雙isoxazoline取代calix[4]arenes的合成研究

Abstract

摘 要 本論文之研究可分為三部份，其目的為利用官能基化法合成不同上緣取代及下緣取代之calix[4]arenes，以利於進行主客化學研究之用。首先，將5,11-diallyl-25,26,27,28-tetrahydroxycalix[4]arene 43、三乙基胺與不同苯環對位取代基之benzohydroximinoyl chloride 41a-e加入acetonitrile中進行1,3-偶極環化加成反應時，當三乙基胺及benzohy-droximinoyl chloride用量較多且反應時間較長時，可得雙加成產物5, 11-diisoxazo-linomethyl-25,26,27,28-tetrahydroxycalix[4]arene 44a-e；當三乙基胺及benzohydroximinoyl chloride用量較少且反應時間較短時，可得單加成產物5-allyl-11-isoxazolinomethyl-25,26,27,28-tetrahydroxy-calix[4]arene 45a-e。 再者是進行有關於上緣為偶氮取代calix[4]arenes之合成研究，我們企圖將不同的alkyl halide引入25,27-diallyloxy-26-benzoyloxy-28-hydroxycalix[4]arene 47以增加溶解度及降低熔點，因此將化合物47與不同的alkyl halide進行醚化反應，將所得產物（48a-c）水解去保護，再將產物（49a-b）及化合物47經由熱誘導Claisen Rearrangement反應，可得到5,17-diallyl-26-alkyloxy-25,27,28-trihydroxycalix[4]arene 50a-b與5,17-diallyl-26-benzoyloxy-25,27,28-trihydroxycalix[4]-arene 51，但因Claisen Rearrangement反應步驟所得產物之產率不如預期，有待進一步研究加以探討。 最後我們進行了含有硫酮之calix[4]arene的合成研究，以試圖增加其嵌合能力，本實驗中我們以25,26,27,28-tetrahydroxycalix[4]arene 7及benzoyl chloride在不同反應條件下得到雙取代產物25,27-dibenzo-yloxy-26,28-dihydroxycalix[4]arene 52或三取代產物25,26,27-tribenzoyloxy-28-monohydroxycalix[4]arene 53，並將化合物52、53以ClO2氧化個別得到25,27-dibenzoyloxy-26,28-calix[4]quinone 54、25,26,27-tribenzoyloxy-28-calix[4]quinone 55，再將化合物55與P4S10反應，可得產物25,26,27-tribenzoyloxy-28-calix[4]dithio-quinone 56。

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.