Calix[4]arenes with narrow rim 2-mercaptoethoxy substituents as potential precursor molecules for metallacages and sensors

Knoblauch, S.; Falana, Olusegun M.; Nam, Jaewook; Roundhill, D. Max; Hennig, H.; Zeckert, Kornelia

doi:10.1016/s0020-1693(99)00577-0

Cited by 16 publications

(8 citation statements)

References 12 publications

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“…28 Hence, to prepare thiol derivatives of tert butylthiacalix [4]arene 5b-d from thioacetates 4b-d, the latter compounds were subjected to alkaline or acid hydrolysis in various media. The alka line hydrolysis was carried out in the presence of potas sium carbonate in a DMF-water mixture.…”

Section: Methodsmentioning

confidence: 99%

Thiacalix[4] arenes with terminal thiol groups at the lower rim: synthesis and structure

et al. 2009

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Methods were developed for the synthesis of ω mercaptoalkoxy derivatives of thiacalix [4] arenes in the 1,3 alternate conformation containing different numbers (2-5) of methylene spacers at the lower rim. The hydrazinolysis of the corresponding thioacetates is the most efficient method for the synthesis of these compounds.Natural and synthetic macrocyclic compounds show promise for studies in the field of supramolecular chemi stry, because the structural features of these compounds are favorable for a sharp enhancement of the complex ation properties due to the formation of multicenter intermolecular interactions with substrates and the pre organization of coordination centers. Calixarenes 1 have additional advantages associated primarily with the unique possibilities of their functionalization and the fine tuning between the three dimensional structures of the host and the desired guest. The use of thiacalix[4]arene 2 (see Refs 1-5) as a molecular platform for the design of intel lectual receptor and self organized supramolecular sys tems is very attractive, because the replacement of the methylene bridges in the classical calixarene by sulfur atoms gives rise to new properties. 3,4,6-11 In this connec tion, it is important to develop approaches to the directed functionalization of this macrocycle, in particular, by introducing organosulfur fragments. The presence of func tional sulfur containing groups at the lower or upper rim of the macrocycle, in addition to four bridging sulfur atoms of the thiacalixarene platform, offers great possi bilities for the design of highly selective host molecules based on thiophilic metal ions, 12 the construction of highly organized nanolayers on the metal surface, 13-17 and the design of sensors based on ion selective electrodes. 18-20 In addition, these sulfur containing groups have a great synthetic potential for further modifications of the macro cyclic structure. * Dedicated to Academician A. I. Konovalov on his 75th birthday. Results and DiscussionIn the present study, we synthesized new O substi tuted thiacalix[4]arenes in the 1,3 alternate conformation containing ω bromo (3), ω acetoxy (4), or ω mercapto alkyl groups (5) linked by methylene spacers of different length (from two to five units). The structures of the new compounds were determined by different physical methods, such as 1D and 2D NMR spectroscopy, IR spectroscopy, and MALDI TOF mass spectrometry. The purity of the compounds was checked by TLC and elemental analysis.CH 2 H 2 S H 3a-e S (CH 2 ) n Br, n = 2 (a), 3 (b), 4 (c), 5 (d), 6 (e) 4a-d S (CH 2 ) n SC(O)CH 3 , n = 2 (a), 3 (b), 4 (c), 5 (d) 5a-d S (CH 2 ) n SH, n = 2 (a), 3 (b), 4 (c), 5 (d)

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Section: Methodsmentioning

confidence: 99%

Thiacalix[4] arenes with terminal thiol groups at the lower rim: synthesis and structure

et al. 2009

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“…BF 4 -stationary phase, the thermodynamic parameters in the retention process of the probe molecules were calculated to elucidate the driving power in the chromatographic retention process. And, the linear solvation energy relationship (LSER) between the solvation solute descriptors and retention factors for the selected probe molecules were analyzed to discuss the interaction forces of the probe molecules with the C [4] The p-tert-butylcalix [4]arene and 5,11,17,23-tetra-tertbutyl-25,26,27,28-tetra-ethoxycarbonylmethyloxy calix [4] arene (C[4]TECM) were prepared in the following manner (Scheme 1) [23,24].…”

Section: Introductionmentioning

confidence: 99%

Characterization of Calixarene/Ionic Liquid Mixture as Gas Chromatographic Stationary Phase through Thermodynamic Parameters and LSER

Shi

Jia

2012

Chromatographia

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A mixture of 5,11,17,23-tetra-tert-butyl-25,26, 27, 28-tetraethoxycarbonylmethyloxy calix[4]arene (C[4] TECM) and 1-octyl-3-methylimidazolium tetrafluoroborate ionic liquid (O m I m ? BF 4 -) has been employed as stationary phases in capillary gas chromatography. Its properties have been characterized through thermodynamic parameters and linear solvation energy relationship. The experimental results showed that C[4]TECM-O m I m ? BF 4 -mixture as gas chromatographic stationary phase has high column efficiency and peak symmetry, which were evaluated using naphthalene and n-octanol, respectively. It was demonstrated that the interaction forces between the probe molecules and the stationary phase did not change over the entire temperature range studied due to an excellent linear relationship between lnk and 1/T, the retentions of the probe molecules on the C[4]TECM-O m I m ? BF 4 -stationary phase are enthalpy-driven processes, and the interactions of the probe molecules with C[4]TECM-O m I m ? BF 4 -stationary phase mainly include hydrogen bonding interaction, dipole-dipole interaction and dispersive interaction. However, the contribution of each interaction is in the order of A [ L [ S for the C[4]TECM-O m I m ? BF 4 -stationary phase.

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“…The structures possess a wide rim with hydrocarbon functionalities and a narrow rim with phenolic groups. Synthetic modifications at these rims can be carried out to introduce desired molecular properties, namely, extra ligands [4,5]. Accordingly, for versatile applications, narrow rim metal-narrow rim, narrow rim metalwide rim or wide rim metal-wide rim cages could be assembled for hosting organic molecules [6 -8].…”

Section: Introductionmentioning

confidence: 99%

“…Accordingly, for versatile applications, narrow rim metal-narrow rim, narrow rim metalwide rim or wide rim metal-wide rim cages could be assembled for hosting organic molecules [6 -8]. Analogously, for the analytical aspects of hazardous heavy metal contaminants, chemosensors based on calixarene metallacage architectures seemed particularly attractive [5]. In this context, we reported the synthesis of chemosensors as an interesting approach providing accurate analytical tools in different analytical fields.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Novel Macrocyclic Peptido-calix[4]arenes and Peptidopyridines as Precursors for Potential Molecular Metallacages, Chemosensors and Biologically Active Candidates

Amr

Abo-Ghalia

Abdalah³

2006

Zeitschrift Für Naturforschung B

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Novel macrocyclic dipicolinic acid acylated peptides based on upper rim bridged peptidocalix[4]arenes, peptido-pyridines or hybrid structures of both, were synthesized as potential molecular metallacages and chemosensors. While conventional azide or mixed anhydride (ethyl chloroformate) peptide couplings served well for assembling the L-tyrosine or L-ornithine peptide backbones, the acid chloride of pyridine-2,6-dicarboxylic acid (dipicolinic acid) acid served as the complementary acylating agent. The structure assignment of the new compounds was based on chemical and spectroscopic evidences. Some of these compounds exhibit antimicrobial activities.

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Calix[4]arenes with narrow rim 2-mercaptoethoxy substituents as potential precursor molecules for metallacages and sensors

Cited by 16 publications

References 12 publications

Thiacalix[4] arenes with terminal thiol groups at the lower rim: synthesis and structure

Thiacalix[4] arenes with terminal thiol groups at the lower rim: synthesis and structure

Characterization of Calixarene/Ionic Liquid Mixture as Gas Chromatographic Stationary Phase through Thermodynamic Parameters and LSER

Synthesis of Novel Macrocyclic Peptido-calix[4]arenes and Peptidopyridines as Precursors for Potential Molecular Metallacages, Chemosensors and Biologically Active Candidates

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