The study in the synthesis of 1,2-diaikoxycalix[4]arenes

• Main Authors: Chiun-Shiang Huang, 黃群翔
• Other Authors: Lee-gin Lin
• Format: Others
• Language: zh-TW
• Published: 2008
• Online Access: http://ndltd.ncl.edu.tw/handle/42672760853103736336

碩士 === 中國文化大學 === 應用化學研究所 === 96 === 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 43-45. In base conditions, p-tert-butylphenol were polymerized with formaldehyde to form a yellowish precursor. Refluxing of this precursor in diphenyl ether yielded the p-tert- butylcalix[4]arene (1). The AlCl3 catalyzed reverse Friedel-Crafts reaction were then applied to removed the p-tere-butyl groups and gave parent the calix[4]arene (6). In our earlier studies on the 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. Esterification of those monoalkylated calix[4]arenes 30-34 with an excess of acetyl chloride in pyridine produced the corresponding diacetate products, 25-alkoxy-26,27-diacetoxy-28-hydroxycalix[4]arenes 35-39. Products 36-38 were treated with K2CO3 and alkyl halides in CH3CN to yielded the 25,26-diacetoxy-27,28-dialkoxycalix[4]arenes 40-42. The removed of acetate moieties in basic conditions was expected to yield the corresponding vicinal 1,2-dialkoxycalix[4]arenes 43-45. 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.