Synthesis and Conformational Studies on [3.3.3]Metacyclophane Oligoketone Derivatives, and Their Metal Ion Recognition

Louis Korbla Doamekpor^1*, Raphael Kwaku Klake¹, Vincent Kodzo Nartey¹, Takehiko Yamato², Oti Gyamfi³, Dennis Adotey³

¹Department of Chemistry, University of Ghana, Accra, Ghana.
²Department of Chemistry, Saga University, Saga, Japan.
³Ghana Atomic Energy Commission, Accra, Ghana.

DOI: 10.4236/ijoc.2015.52014                

Abstract

Chemical reactions were used to synthesize 2,11,20-tris(ethanedithia)-9,18,27-trimethoxy-6,15, 24-tri-tert-butyl[3.3.3]metacyclophane 2 and 2,11-bis(ethanedithia)-9,18,27-trimethoxy-6,15,24-tri-tert-butyl[3.3.3]metacyclophane 4 from 6,15,24-tri-tert-butyl-9,18,27-trimethoxy[3.3.3]meta-cyclophane-2,11,20-trione 1 and -2,11-dione 3. The yields of 2 and 4 were 70% and 81% respectively. The conformations of the synthesized compounds 2 and 4 were studied using mainly solution Proton Nuclear Magnetic Resonance (¹H NMR) spectroscopic methods. Compounds 2 and 4 were found to have a partial-cone conformation. Detailed variable temperature Proton Nuclear Magnetic Resonance studies further confirmed the partial-cone conformation for the two products, 2, 4. During the variable temperature nuclear magnetic resonance spectroscopic studies, compound 2 was found to have a coalescence temperature of about 0?C. Extraction of silver ions with compound 2 gave an extractability of 82% while the parent compound 1 showed zero (0) silver affinity. A 1:1 mol/mol mixture of compound 2 and silver ions studied by solution 1H NMR revealed a novel “Molecular Roulette” type of motion.

Keywords

Metacyclophanes, Macrocyclic Compounds, Cone, Partial-Cone, Conformation, Variable Temperature Proton Nuclear Magnetic Resonance Spectroscopy, Coalescence Temperature

Conflicts of Interest

The authors declare no conflicts of interest.

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