Chemistry and Biochemistry DepartmentThesis Defense

THE INVESTIGATION OF BIS-(β-DIKETONES) AS MONOMERS IN THE SYNTHESIS OF COORDINATION POLYMERS

Yu-Liang HsuehABSTRACT

β-diketones are a family of compounds that are famous for their interesting chemical and

physical properties, in addition to their keto-enol tautomerism. The simplest aliphatic β-

diketone is known as acetylacetone (Hacac, 2, 4-pentanedione), which forms strongly-

bound complexes with multiple metal cations (alkali and transition metals). This strong

complexation allows bis-(β-diketones) to be monomers for the synthesis of coordination

polymers. The goal is to explore the best methods to prepare bis-(β-diketones) in large

scale for the future synthesis of coordination polymers. Percent yield, ease of synthesis

(one step synthesis), product purity and versatility of derivatives have been considered as

the criteria for the ideal monomers. The following synthetic routes have been explored to

prepare the bis-(β-diketones): (1) condensation of Hacac and formaldehyde produces 3,5-

diacetyl-2,6-heptanedione (H2L1); (2) 3,5-diacetyl-4-phenyl-2,6-heptanedione (H2L2) was

synthesized by Knoevenagel condensation of benzaldehyde and Hacac; (3) the crossed

Claisen condensation of a ketone and an ester has been adopted to prepare 1,4-bis-(3-

phenyl-3-oxopropionyl)benzene (H2L3); finally, (4) reaction of leucoquinizarin and

butyraldehyde produces 2-butylquinizarin (H2L4) through aldol condensation. This aldol

condensation is an efficient route giving high percent yield.

Committee Members: Wednesday, June 1, 2016

Dr. Floyd Klavetter (Chair) 8:20 – 10:00 AM

Dr. Chantal Stieber Building: 4/1-314

Dr. Gregory A. Barding Jr.