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

• 作者: Dennis Adotey Louis Korbla Doamekpor Oti Gyamfi Raphael Kwaku Klake Takehiko Yamato Vincent Kodzo Nartey
• 来源期刊: 有机化学国际期刊(英文)
• 学科: 化学
• 关键词: Metacyclophanes MACROCYCLIC Compounds CONE Partial-Cone CONFORMATION Variable TEMPERATURE Proton Nuclear Magnetic Resonance Spectroscopy COALESCENCE TEMPERATURE
• 年，卷（期）: 2015,（2）
• 页码范围: 126-135
• 页数: 10页
• 分类号: O6

摘要

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.