Synthesis of molecular containers based on modifications of resorcin(4)arene and calix(4)arene

Abstract

This research work was mainly focused on the synthesis of molecular containers based on modifications ofresorcin[4]arene and calix[4]arene.

The modifications of resorcin[ 4 ]arene include the attempts to attach a phthalimide featured linker onto the phenol hydroxyl groups of resorcin[4]arene. A few halogen leaving groups were used, including fluorine, chlorine, and bromine. The substitution with tetraflorophthalimide resulted in a mixture of regio-isomeric products, whereas for 4,5-dichloro- and 4,5-dibromophthalimides, no desired substitution product was formed. It was, however, discovered that both 4,5-dichloro- and 4,5-dibromophthalimides forms monoclinic crystals. The second modification of resorcin[4]arene focused on functionalizations of both upper and lower rims of this basket-shaped potential host molecule. 2,6-Dihydroxybenzyl alcohol was prepared in a overall yield of 24% in two steps, in order to introduce a derivative of resorcinol. On the other hand, 4- benzyloxybutanal was synthesized by a Swem oxidation of 4-benzyloxybutanol in 10% yield. The attempt of 4-benzyloxybutanal reacting with resorcinol was, however, proved unsuccessful.

The modifications of calix[4]arene involved an extensive study of mono- and difunctionalization of both aliphatic (1,4-butanediol and 1, 10-decanediol) and aromatic (benzene 1,4-dimethanol) diols. Tosyl group, silyl group, benzyl group as well as bromine, have been used to transform the diols into corresponding products in various percent yields. The monofunctinoalized 4-(p-toluenesulfonyl)butanol and 10-(p-toluenesulfonyl)decanol was obtained in a yield of 30-46% using a solvent-free method. The desired monofunctionalized products were obtained when excess of the diols were used. On the other hand, excess 4-Benzene dimethanol was treated with HBr resulted monobrominated product with 48% yield. The mono-tosylated diols was found not a good substrate for substitution with calix[4]arene, whereas the substitution bromide, such as 1-bromobutane, did work, which has led to the desired dimer of calix[4]arene.

Date of Award	2011
Original language	American English
Awarding Institution	Eastern Illinois University
Supervisor	Zhiqing Yan (Supervisor)