| Summary: | 碩士 === 中國文化大學 === 應用化學研究所 === 95 === Calixarenes, which are cyclic oligomers of p-substituted phenols and formaldehyde, are able to include small organic molecules or metal ions within the molecular cavities to form ‘‘ host-guest ’’ complexes. These phenomena have been proposed in the applications of micro- analysis, ion separation, and enzyme-mimic studies. The main purpose of this thesis is to study the synthesis of calix[4]arene 1,2-dialkyl ethers.
In the presence of a base, p-tert-butylphenol and formaldehyde were polymerized to form a yellowish precursor. Refluxing of this precursor in diphenyl ether for two hours yielded the p-tert- butylcalix[4]arene (1). The p-tert-butyl groups were then removed by AlCl3 catalyzed reverse Friedel-Crafts reaction to give parent calix[4]arene (6).
In our earlier studies on the series of calix[4]arene ethers, we have noticed that in the presence of sodium methoxide as the reacting base,the monoalkylated calix[4]arenes can be prepared by refluxing calix[4]arene with alkyl halides in CH3CN. Five different alkyl halides, iodoethane, 1-iodopropane, 1-iodobutane, allyl bromide, and benzyl bromide, were applied in this synthetic procedure.
The esterification of those monoalkylated calix[4]arenes 30-34
with an excess acetyl chloride in pyridine produced the corresponding 25-alkoxy-26,27-diacetoxy-28-hydroxycalix[4]arenes 35-39. Products 35-39 were further treated with K2CO3 and alkyl halides in CH3CN to yielded the 25,26-diacetoxy-27,28-dialkoxycalix[4]arenes 40-44. The acetate moieties were then removed in basic hydrolysis condition to give the vicinal 1,2-dialkoxycalix[4]arenes.
All the new products which were produced in this thesis were characterized by 1H-NMR, 13C-NMR, COSY, and FAB-MS. The synthetic procedure for vicinal 1,2-dialkoxycalix[4]arenes were also discussed in this thesis.
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