Synthesis of p-tert-butylthiacalix[4]arene and its inclusion property
TL;DR: In this paper, a practical method for the synthesis of p-tert-butylthiacalix[4]arene (TC4A), in which the methylene bridges of C4A are replaced by epithio groups, is presented by heating a mixture of ptert butylphenol, elemental sulfur S8, and NaOH as a base catalyst in tetraethylene glycol dimethyl ether.
About: This article is published in Tetrahedron.The article was published on 2000-03-10. It has received 233 citations till now. The article focuses on the topics: Tetraethylene glycol dimethyl ether & Substituent.
Citations
More filters
TL;DR: In this paper, the chemistry of thiacalixarenes, a new member of the calixarene family with four sulfur atoms in the place of methylene groups, is discussed.
294 citations
TL;DR: These novel macrocycles, which belong to the next generation of calixarenes or cyclophanes, form a unique cavity that is resulted from two isolated benzene planes and two bis-heteroatom-conjugated triazine planes in a 1,3-alternate fashion.
Abstract: A number of aza- and/or oxo-bridged calix[2]arene[2]triazines have been synthesized through an unusually high yielding and efficient fragment coupling approach starting from cyanuric chloride and resorcinol, 3-aminophenol, m-phenylenediamine, and N,N'-dimethyl-m-phenylenediamine. These novel macrocycles, which belong to the next generation of calixarenes or cyclophanes, form a unique cavity that is resulted from two isolated benzene planes and two bis-heteroatom-conjugated triazine planes in a 1,3-alternate fashion. The nature of the bridging heteroatoms, i.e., combination of the electronic, conjugative, and steric effects of the nitrogen and oxygen atoms, strongly regulates the cavity size, generating a set of fine-tuned cavities in which the distance between two benzene rings at the upper rim ranges from 5.011 to 7.979 A. The multiple intermolecular hydrogen bond interactions among N,N'-dimethylated tetraazacalix[2]arene[2]triazines and among tetraazacalix[2]arene[2]triazines lead to the formation of infinite one-dimensional chain structure and two-dimensional zigzag layered structure, respectively, in the solid state. The ease of preparation and further chemical manipulations, and the readily tunable cavity structures render these aza- and/or oxo-bridged calix[2]arene[2]triazines the unique platforms in the study of supramolecular chemistry.
245 citations
TL;DR: Results indicated that incorporation of thiacalix[4]arene tetrasulfonate and Fe3O4 into sodium alginate nanoparticles increased the adsorption capacity of sodiumAlginate bioadsorbents, and led to the magnetic property.
178 citations
TL;DR: In this paper, the authors present the results of their own study to demonstrate the potentials over the limits of the conventional calixarenes, putting emphasis on the indispensable role of the bridging sulfur.
Abstract: Heteroatom-bridged calixarenes have been confined intothe unexplored frontier of the vast realm of the calixarene chemistry because of their syntheticdifficulty. Since we found facile one-step synthesis of thiacalix[4]arene, in which four methylenebridges of calix[4]arene are replaced by four sulfides, we have been engaged in the study on thisnew molecular platform regarding the improvements for the synthetic procedures, structuralanalyses, chemical modifications, and functional developments. In this review are describedthe results of our own study to demonstrate the potentials over the limits of the conventionalcalixarenes, putting emphasis on the indispensable role of the bridging sulfur. Highlighted examples are(1) enlargement of the calix skeleton to provide larger cavity, (2) ready oxidizability to sulfoxideand sulfone for providing new members of S bridged calixarenes, and (3) coordination to specificmetal ions controlled by the oxidation state of S. These indicate a hopeful future for thethiacalixarene platform in the forthcoming applications to functional molecular devices.
169 citations
TL;DR: The photoluminescent analyses suggest that there is an efficient ligand-to-Ln(III) energy transfer for compounds 1-3 and H(4)PTC4A is a more efficient "antenna" than H( 4)TC4B.
Abstract: This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear TbIII (1 and 3) and DyIII (2 and 4) complexes supported by p-phenylthiacalix[4]arene (H4PTC4A) and p-tert-butylthiacalix[4]arene (H4TC4A). All four frameworks can be formulated as [LnIII4(PTC4A/TC4A)2(μ4-OH)Cl3(CH3OH)2(H2O)3], and some methanol and water solvent molecules are occupied in the interstices. The compounds are featured with a sandwichlike unit constructed by two tail-to-tail calixarene molecules and a planar tetragonal (μ4-OH)Ln4 cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-LnIII energy transfer for compounds 1−3 and H4PTC4A is a more efficient “antenna” than H4TC4A. The DyIII compounds exhibit slow magnetic relaxation behavior of single-molecule magnet nature. The substitution of the t-Bu group with a phenyl group at the up-rim of thiacalix[4]arene leads to different extended structures and physical properties of as-synthesized compounds.
144 citations
References
More filters
TL;DR: In this paper, the condensation reaction between p-tert-butylphenol and formaldehyde leads in a single step to good yields of cyclic oligomers in which, depending on the reaction conditions, either four, six, or eight phenol units are joined by methylene bridges.
Abstract: The condensation reaction between p-tert-butylphenol and formaldehyde leads in a single step to good yields of cyclic oligomers in which, depending on the reaction conditions, either four, six, or eight phenol units are joined by methylene bridges. The beakerlike shape of the most stable conformation of the tetramer has led to their being given the name “calixarenes” (calix = chalice). Resorcinol can undergo condensation in a similar manner with a variety of aldehydes to afford cyclic tetramers with the same basic structure (the resorcarenes). In both cases the reaction does not require the use of dilution techniques, so that large quantities of product can be readily obtained. In addition, the parent compounds can be modified in various ways, in particular at the phenolic hydroxy groups or the phenyl residues; these approaches can be used separately or in combination. Calixarenes are thus ideal starting materials for the synthesis of various types of host molecules and can also act as building blocks for the construction of larger molecular systems with defined structures and functions. Their potential applications range from use as highly specific ligands for analytical chemistry, sensor techniques and medical diagnostics to their use in the decontamination of waste water and the construction of artificial enzymes and the synthesis of new materials for non-linear optics or for ultrathin layers and sieve membranes with molecular pores.
1,744 citations
Book•
27 Sep 2011
TL;DR: In this paper, the authors present a single-step approach to synthesize Calixarenes in the solid state and show the properties of the resulting Calix-arenes.
Abstract: One: History and Synthesis of Calixarenes.- Single Step Synthesis and Properties of Calixarenes.- 1. Introduction.- 2. Single Step Synthesis of Calixarenes.- 2.1. Base-Induced Procedures.- 2.2. Acid-Catalyzed Procedures.- 2.3. Thermally Induced Procedures.- 3. Synthesis of Functionalized Calixarenes.- 3.1. Introduction of Substituents on the 'Lower Rim' of Phenol-Derived Calixarenes.- 3.1.1. Ester and Ether Formation with Monofunctionalized Reagents.- 3.1.2. Esterification and Etherification with Polyfunctionalized Reagents.- 3.2. Introduction of Substituents on the 'Upper Rim' of Phenol-Derived Calixarenes.- 3.2.1. Dealkylation of p-Alkylcalixarenes.- 3.2.2. Electrophilic Substitution Route.- 3.2.3. p-Claisen Rearrangement Route.- 3.2.4. p-Quinonemethide Route.- 3.2.5. p-Chloromethylation Route.- 3.3. Introduction of Substituents at the 'Upper Rim' of Resorcinol-Derived Calixarenes.- 3.4. Introduction of Functional Groups at the Methylene Bridges of Calixarenes.- 4. Physical Properties of Calixarenes.- 4.1. Melting Points.- 4.2. Solubilities.- 4.3. Spectral Properties of Calixarenes.- 4.3.1. Infrared Spectra.- 4.3.2. Ultraviolet Spectra.- 4.3.3. NMR Spectra.- 4.3.4. Mass Spectra.- 5. Concluding Comments.- References.- Special Calixarenes, Synthesis and Properties.- 1. Introduction.- 2. Stepwise Synthesis of Calixarenes.- 3. Fragment Condensation.- 4. Selective Functionalization.- 5. The First Acidity Constant of Calix[4]arenes.- 6. Chiral Calix[4]arenes.- 7. Bridged Calixarenes.- 8. Double Calixarenes and Future Directions.- References.- Two: X-Ray Structural Data on Calixarene Architectures.- Conformations of Calixarenes in the Crystalline State.- 1. Introduction.- 2. Conformations and Structures of Some Precursors.- 3. Conformations of Calixarenes.- 3.1. Introduction.- 3.2. Conformations of Calix[4]arenes.- 3.2.1. Calix[4]arenes with a Fourfold Axis.- 3.2.3. Calix[4]arenes with Symmetry Planes.- 3.2.3. Calix[4]arenes with a Twofold Axis.- 3.2.4. Calix[4]arenes in the Cone Conformation with No Particular Symmetry.- 3.3. Conformations of Calix[5]arenes.- 3.4. Conformations of Calix[6]arenes.- 3.4.1. Calix[6]arenes with Symmetry Planes.- 3.4.2. Calix[6]arenes in the Centrosymmetrical Conformation.- 3.5. Conformations of Calix[7]arenes.- 3.6. Conformations of Calix[8]arenes.- 3.6.1. Calix[8]arenes with Mirror Planes.- 4. Conclusion.- References.- Inclusion Properties and Host-Guest Interactions of Calixarenes in the Solid State.- 1. Introduction.- 1.1. General Considerations.- 1.2. Conformational Properties of Calixarenes in the Solid State.- 2. Conformational Preferences in Functionalized Calixarenes.- 2.1. Calix[4]arenes.- 2.2. Calix[6]arenes.- 2.3. Calix[8]arenes.- 2.4. Calixarene Cavitands.- 3. Metallocalixarenes.- 4. Calixarene Based Cation Carriers and Receptors.- 5. Molecular Inclusion of Neutral Molecules by Calixarenes.- 5.1. Intramolecular Complexes of Calixarenes.- 5.2. Cage Complexes.- 5.3. Intermolecular Complexes.- 5.4. Clathrates.- 6. Theoretical Models for the Host-Guest Interactions.- Acknowledgements.- References.- Three: Inclusion Properties of Calixarenes and Their Derivatives.- Calixarene-Based Cation Receptors and Carriers.- 1. Introduction.- 2. Calixarene Podands with Ether Chains.- 3. Calixarene Podands with Ester and Amide Groups.- 4. Calixcrowns and Calixspherands.- 5. Ionizable Calixarene Ligands.- 6. Concluding Remarks.- Acknowledgements.- References.- Chemically Modified Calixarenes as New Selective Receptors for Monovalent Cations.- 1. Introduction.- 2. Calixarenes as Receptor Substructures.- 3. Chemically Modified Calixarenes.- 4. Complexation of Alkali Cations: Phase Transfer, Stability Constants, Selectivities, and Transport.- 4.1. Calixarene Esters and Ketones.- 4.1.1. Extraction Experiments.- 4.1.2. Stability Constants.- 4.1.3. Complexation Selectivities.- 4.1.4. Ion Transport.- 4.2. Calixarene Amides.- 4.3. Calixarenes with Mixed Ligating Functional Groups.- 4.4. Relation between Physicochemical Properties and Molecular Structure.- 5. Conclusions and Perspectives.- Acknowledgements.- References.- Functionalized Calixarenes: New Applications as Catalysts, Ligands, and Host Molecules.- 1. Introduction.- 2. Syntheses of Functionalized Calixarenes.- 3. Conformational Properties.- 4. Acidity Constants of the Phenolic Hydroxyl Groups.- 5. Aggregation and Inclusion Phenomena.- 6. Chiral Calixarenes.- 7. Ionophoric Calixarenes.- 8. Conclusions.- References.- Water Soluble Calixarene Salts. A Class of Compounds with Solid-State Structures Resembling Those of Clays.- 1. Introduction.- 2. The [Calix[4]arene Sulfonate]5- Anion.- 2.1. Na5[Calix[4]arene Sulfonate].- 2.2. Other Alkali Salts.- 2.3. Transition Metals and Lanthanides.- 2.4. Inclusion of Organic Species.- 3. The [Nitrocalix[4]arene]2- Anion.- 4. The [Calix[4]arene Sulfonate Methyl Ether]4- Anion.- References.- Lanthanide Ions and Calixarenes.- 1. Introduction.- 2. Lanthanide Ions and p-fert-Butylcalixarenes.- 2.1. Synthesis and Stoichiometry.- 2.1.1. Complexes of p-tert-Butylcalix[8]arene.- 2.1.2. Complexes of p-tert-Butylcalix[6]arene.- 2.1.3. Complexes of p-tert-Butylcalix[4]arene and p-tert-Butylbishomooxacalix[4]arene.- 2.2. Solid State Structures - X-Ray Crystallography.- 2.2.1. Complexes of p-tert-Butylcalix[8]arene.- 2.2.2. Complexes of p-tert-Butylcalix[6]arene.- 2.2.3. Complexes of p-tert-Butylcalix[4]arene.- 2.3. Solution Structure.- 2.4. Luminescence Spectroscopy.- 3. Conclusions.- Acknowledgements.- References.- Four: Industrial Applications.- Industrial Applications of Calixarenes.- 1. Introduction.- 2. Recovery of Cesium.- 3. Recovery of Uranium.- 4. Further Ion Sequestering Possibilities.- 5. Ion Selective Electrodes and Field Effect Transistors.- 6. Phase Transfer Agents.- 7. Accelerators for Instant Adhesives.- 8. Ion Scavengers for Electronic Devices.- 9. Stabilizers for Organic Polymers.- 10. Separation of Neutral Organic Molecules.- 11. Hydrolysis Catalysts.- 12. Langmuir-Blodgett Films and Membranes.- 13. Polymer-Bound Calixarenes.- 14. Concluding Remarks.- References.- List of Contributors.
939 citations
TL;DR: In this paper, the tetrameric structure of the low melting point product obtained from the base catalysed condensation of formaldehyde and para-t-butylphenol and its ability to form a stable cage-type clathrate with toluene was analyzed.
Abstract: Single-crystal X-ray analysis has shown the tetrameric structure of the low melting point product obtained from the base catalysed condensation of formaldehyde and para-t-butylphenol and its ability to form a stable cage-type clathrate with toluene.
234 citations
TL;DR: In this article, the synthesis of tetrathiacalix[4]arene was achieved by detertiobutylation of p-tert-butyltetrathiatectetrathiaalix [4]-arene.
191 citations
TL;DR: In this paper, the four methylene birdge of calix[4]arenes are replaced by sulfide linkages, and they were selectively oxidized to sulfinyl- or sulfonylcalix[ 4]arene under mild conditions with control of the stoichiometry of the oxidant.
167 citations