Graduate Program
Chemistry
Degree Name
Master of Science (MS)
Semester of Degree Completion
2011
Thesis Director
Zhiqing Yan
Thesis Committee Member
Daniel Sheeran
Thesis Committee Member
Edward Treadwell
Thesis Committee Member
Radu Semeniuc
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.
Recommended Citation
Makineni, Anupama, "Synthesis of molecular containers based on modifications of resorcin(4)arene and calix(4)arene" (2011). Masters Theses. 748.
https://thekeep.eiu.edu/theses/748
