| Summary: | 碩士 === 中國文化大學 === 化學系應用化學碩士班 === 102 === Calixarenes, which are cyclic oligomers of p-substituted phenols and formaldehyde, are able to include small organic molecules or metal ions within molecular cavities to form the “host-guest complexes”. This phenomenon has been proposed in the research area of micro-analysis detection devices, ion separation, and enzyme-mimic studies. The main purpose of this thesis is to study the benzoyl-migration behavior in 1-ethoxy-3-benzoyloxycalix[4]arenes and 1-benzyloxy-3-benzoyloxy-
calix[4]arenesystems.
In the present of a base, p-tert-butylphenol and formaldehyde were polymerized to form a yellowish precursor. Refluxing the precursor in diphenyl ether yielded the p-tert-butylcalix[4]arene. The p-tert-butyl groups were then removed via AlCl3-catalyzed reverse Friedel-Crafts reaction to give the calix[4]arene (6).
In our earlier studies, we have noticed that in the present of sodium methoxide,the the calix[4]arene can be converted to monoalkyloxycalix[4]arenes (27-31) by refluxing with different kind of alkyl halides in acetonitrile.
Esterification of the monoalkylated calix[4]arenes (27-31) with excess of benzoyl chloride or p-substituted benzoyl chlorides in pyridine produced the corresponding 1-alkoxy-3-benzoyloxycalix[4]arenes (32-35). The 1-alkoxy-3-benzoyloxycalix[4]arenes (32-35) were then conrected to 1-alkoxy-3-benzoyloxycalix[4]arenes(36-39) under basic condition.
The kinetic property of the benzoyl-migration was investigated, and the benzoyl-migrated products were isolated and characterized by 1H-NMR
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