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  • 1
    ISSN: 0947-6539
    Keywords: calixarenes ; cavitands ; molecular modeling ; resorcinarenes ; supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coupling reactions of calix[4]arenes and modified resorcin[4]arenes have been investigated. Reaction of mono(chloroacetamido)calix[4]arene 4 with tetrahydroxycavitand 9 gave the 1:1 coupled product 13 in 61% yield. Combination of upper-rim 1,3-difunctionalized calix[4]arene 5 with 9 afforded predominantly the 2:1 calix-resorcinarene 18 in 47% yield. Reaction of 1,2-difunctionalized calix[4]arene 6 with 9 gave five products, namely, endo 1:1 (19), exo 1:1 (20), endo-endo 2:1 (21), endo-exo 2:1 (22), and exo-exo 2:1 (23) in ratios that depend on the reaction conditions. The stereochemistry of the different products was determined with NOESY experiments. The structures of 21 a and 23 b were calculated by using molecular mechanics, which revealed that intramolecular hydrogen bonds are only present in the former. Reaction of 1,2-bis(chloroacetamido)calix[4]arene 26, which has two additional nitro groups at the remaining aromatic rings, with 9 yielded three different products, namely, endo 1:1 (28), endo-endo 2:1 (30), and endo-exo 2:1 (32) in ratios that depend on the reaction conditions. There is a preference for the endo orientation in the formation of the 1:1 coupled product, probably owing to an interaction of the nitro groups with the cavitand in the transition state. After conversion of the nitro groups in 28 into chloroacetamido moieties, reaction with Cs2CO3 in DMF under high-dilution conditions afforded holand 33 in 26% yield together with calix[4]arene-based carceplex 34 with an encapsulated DMF molecule (27% yield). Holand 33 was obtained in 33% yield by reaction of the tetrakis(chloroacetamide) endo-endo 2:1 isomer 31 with tetrahydroxycavitand 9. Holand 33 contains a cavity of nanosize dimensions. Molecular mechanics simulations indicate that holand 33 adopts a conformation with eight hydrogen bonds and a large, preorganized cavity with two entrances of smaller dimensions. Molecular dynamics simulations of holand 33 in both CHCl3 and THF showed that four solvent molecules can be accommodated in the cavity at well-defined positions.
    Additional Material: 11 Ill.
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  • 2
    ISSN: 0947-6539
    Keywords: calixarenes ; carcerands ; inclusion compounds ; molecular devices ; resorcinarenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 11 calix[4]arene-based carceplexes obtained by solvent or doped inclusion is reported. Carceplexes with amides, for example, DMF, NMP, and 1,5-dimethyl-2-pyrrolidinone, and sulfoxides, for example, DMSO and thiolane-1-oxide, were obtained by solvent inclusion. In these cases the yield of the carceplex decreases with increasing guest size. Potential guests that do not form carceplexes by solvent inclusion, such as 2-butanone and 3-sulfolene, could be incarcerated by doped inclusion with 1,5-dimethyl-2-pyrrolidinone as a solvent “doped” with 5-15 vol% of potential guest. The amide bridges of the carceplexes were converted into thioamide bridges in essentially quantitative yield by means of Lawesson's reagent in refluxing xylene. The dynamic properties of the incarcerated guests were examined by 2D NMR spectroscopy. Whereas for most guests a preference for one orientation inside the calix[4]arene-based (thia)carcerands was observed, for DMA, NMP, and ethyl methyl sulfoxide inside calix[4]arene-based (thia)carcerands two different orientations were present. The energy barriers for interconversion between the various orientations of DMA, NMP, and ethyl methyl sulfoxide inside calix[4]arene-based (thia)-carcerands were determined with 2D EXSY NMR. The energy barriers are higher for the thiacarcerands than for the corresponding carcerands with amide bridges. This may be due to the stronger hydrogen-bond-donating character of the thioamide group. Furthermore, molecular modeling simulations indicate that in case of the thiacarcerand the cavity is smaller as a result of a smaller diametrical distance between the NH atoms. Our results demonstrate that molecular modeling can be used to estimate the energy barriers for interconversion; the calculated activation energies showed good quantitative agreement with the experimental values.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2689-2702 
    ISSN: 1434-193X
    Keywords: Modular approach ; Building blocks ; Supramolecular chemistry ; Calix[4]arenes ; Resorcin[4]arenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This review describes covalent and non-covalent combinations of building blocks, e.g. calix[4]arenes, resorcin[4]arenes, cyclodextrins, porphyrins, and cyclotriveratrylenes, leading to well-defined large (receptor) molecules.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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