Various [3.3.3]metacyclophane derivatives were synthesized from 6,15,24-tri-tert-butyl-9,18,27-trimethoxy [3.3.3] metacyclophane-2,11,20-trione 1 using simple chemical reactions. The conformations of the synthesized c...Various [3.3.3]metacyclophane derivatives were synthesized from 6,15,24-tri-tert-butyl-9,18,27-trimethoxy [3.3.3] metacyclophane-2,11,20-trione 1 using simple chemical reactions. The conformations of the synthesized compounds were studied using mainly solution Proton Nuclear Magnetic Resonance (1H NMR) spectroscopic methods. Two of the synthesized compounds 5, 6, were found to have a partial cone conformation with the third, 4, having the cone conformation. Detailed variable temperature Proton Nuclear Magnetic Resonance studies further confirmed the partialcone conformation for the two products, 5, 6. During the variable temperature nuclear magnetic resonance spectroscopic studies, 6,15,24-tri-tert-butyl-9,18,27-trimethoxy[3.3.3]metacyclophane-2,11,20-triol was found to have a coalescence temperature of about 0?C.展开更多
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]metacy...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.展开更多
[1_n]metacyclophanes are a class of important building blocks for supramolecular assembly of artificial capsules. Herein we present the preparation and properties of a novel polyfluorinated macrocycle metaWreath Arene...[1_n]metacyclophanes are a class of important building blocks for supramolecular assembly of artificial capsules. Herein we present the preparation and properties of a novel polyfluorinated macrocycle metaWreath Arene, a C_(2)-symmetrical [14]metacyclophane. Adopting a cone conformation in acetone solution,the macrocycle can form dimer capsules through hydrogen bonds induced by chloride anions. Each dimer capsule consists of two meta-Wreath Arene and two chloride anions, and has been unambiguously characterized both in solution and in solid state.展开更多
文摘Various [3.3.3]metacyclophane derivatives were synthesized from 6,15,24-tri-tert-butyl-9,18,27-trimethoxy [3.3.3] metacyclophane-2,11,20-trione 1 using simple chemical reactions. The conformations of the synthesized compounds were studied using mainly solution Proton Nuclear Magnetic Resonance (1H NMR) spectroscopic methods. Two of the synthesized compounds 5, 6, were found to have a partial cone conformation with the third, 4, having the cone conformation. Detailed variable temperature Proton Nuclear Magnetic Resonance studies further confirmed the partialcone conformation for the two products, 5, 6. During the variable temperature nuclear magnetic resonance spectroscopic studies, 6,15,24-tri-tert-butyl-9,18,27-trimethoxy[3.3.3]metacyclophane-2,11,20-triol was found to have a coalescence temperature of about 0?C.
文摘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.
基金Financial support from the National Natural Science Foundation of China (Nos. 21922113, 22071257, 21988102)Chinese Academy of Sciences (No. XDB17000000)+1 种基金the National Key Research and Development Program (No. 2017YFA0206903)the TIPC Director's Fund。
文摘[1_n]metacyclophanes are a class of important building blocks for supramolecular assembly of artificial capsules. Herein we present the preparation and properties of a novel polyfluorinated macrocycle metaWreath Arene, a C_(2)-symmetrical [14]metacyclophane. Adopting a cone conformation in acetone solution,the macrocycle can form dimer capsules through hydrogen bonds induced by chloride anions. Each dimer capsule consists of two meta-Wreath Arene and two chloride anions, and has been unambiguously characterized both in solution and in solid state.
