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Calix[4]arene‐Based (Hemi)carcerands and Carceplexes: Synthesis, Functionalization, and Molecular Modeling Study
Author(s) -
van Wageningen André M. A.,
Timmerman Peter,
van Duynhoven John P. M.,
Verboom Willem,
van Veggel Frank C. J. M.,
Reinhoudt David N.
Publication year - 1997
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19970030421
Subject(s) - chemistry , thioamide , amide , solvent , calixarene , yield (engineering) , sulfoxide , hydrogen bond , reagent , polymer chemistry , proton nmr , medicinal chemistry , organic chemistry , molecule , materials science , metallurgy
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 N H 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.