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Volumn 3, Issue 4, 1997, Pages 639-654

Calix[4]arene-based (hemi)carcerands and carceplexes: Synthesis, functionalization, and molecular modeling study

Author keywords

calixarene; carcerands; inclusion compounds; molecular devices; resorcinarenes

Indexed keywords


EID: 0030910727     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.19970030421     Document Type: Article
Times cited : (63)

References (87)
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    • b) K. A. Muskat, Photochromism and Thermochromism in Bianthrones and Bianthrylidenes, in The Chemistry of Quinonoid Compounds, Vol. 2 (Eds.: S. Patai, Z. Rappoport), Interscience, London, 1988, and references cited therein.
    • (1988) The Chemistry of Quinonoid Compounds , vol.2
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    • Container Molecules and their Guests
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    • For reviews see: a) D. J. Cram, J. M. Cram, Container Molecules and their Guests, in Monographs in Supramolecular Chemistry, Vol. 4 (Ed.: J. F. Stoddart). Royal Society of Chemistry, Cambridge, 1994; b) J. C. Sherman, Tetrahedron 1995, 51, 3395.
    • (1994) Monographs in Supramolecular Chemistry , vol.4
    • Cram, D.J.1    Cram, J.M.2
  • 19
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    • For reviews see: a) D. J. Cram, J. M. Cram, Container Molecules and their Guests, in Monographs in Supramolecular Chemistry, Vol. 4 (Ed.: J. F. Stoddart). Royal Society of Chemistry, Cambridge, 1994; b) J. C. Sherman, Tetrahedron 1995, 51, 3395.
    • (1995) Tetrahedron , vol.51 , pp. 3395
    • Sherman, J.C.1
  • 20
    • 33751156583 scopus 로고
    • A noncentrosymmetric resorcin[4]arene-based carcerand with different pendant groups was reported by Sherman et al. The cavity, however, is still symmetric. See: J. R. Fraser, B. Borecka, J. Trotter, J. C. Sherman, J. Org. Chem. 1995, 60, 1207.
    • (1995) J. Org. Chem. , vol.60 , pp. 1207
    • Fraser, J.R.1    Borecka, B.2    Trotter, J.3    Sherman, J.C.4
  • 23
    • 0000378992 scopus 로고
    • Preliminary results concerning calix[4]arene-based carcerands were published as communications: a) P. Timmerman, W. Verboom, F. C. J. M. van Veggel, J. P. M. van Duynhoven, D. N. Reinhoudt, Angew. Chem. 1994, 106, 2437; Angew. Chem. Int. Ed. Engl. 1994, 33, 2345; b) A. M. A. van Wageningen, J. P. M. van Duynhoven, W. Verboom, D. N. Reinhoudt, J. Chem. Soc. Chem. Commun. 1995, 1941.
    • (1994) Angew. Chem. , vol.106 , pp. 2437
    • Timmerman, P.1    Verboom, W.2    Van Veggel, F.C.J.M.3    Van Duynhoven, J.P.M.4    Reinhoudt, D.N.5
  • 24
    • 33748243226 scopus 로고
    • Preliminary results concerning calix[4]arene-based carcerands were published as communications: a) P. Timmerman, W. Verboom, F. C. J. M. van Veggel, J. P. M. van Duynhoven, D. N. Reinhoudt, Angew. Chem. 1994, 106, 2437; Angew. Chem. Int. Ed. Engl. 1994, 33, 2345; b) A. M. A. van Wageningen, J. P. M. van Duynhoven, W. Verboom, D. N. Reinhoudt, J. Chem. Soc. Chem. Commun. 1995, 1941.
    • (1994) Angew. Chem. Int. Ed. Engl. , vol.33 , pp. 2345
  • 25
    • 37049077789 scopus 로고
    • Preliminary results concerning calix[4]arene-based carcerands were published as communications: a) P. Timmerman, W. Verboom, F. C. J. M. van Veggel, J. P. M. van Duynhoven, D. N. Reinhoudt, Angew. Chem. 1994, 106, 2437; Angew. Chem. Int. Ed. Engl. 1994, 33, 2345; b) A. M. A. van Wageningen, J. P. M. van Duynhoven, W. Verboom, D. N. Reinhoudt, J. Chem. Soc. Chem. Commun. 1995, 1941.
    • (1995) J. Chem. Soc. Chem. Commun. , pp. 1941
    • Van Wageningen, A.M.A.1    Van Duynhoven, J.P.M.2    Verboom, W.3    Reinhoudt, D.N.4
  • 26
    • 85036448214 scopus 로고    scopus 로고
    • note
    • Cram et al. use the name (hemi)carcerand for the compounds obtained by combination of two resorcin[4]arenes. Since our compounds, obtained by combination of a calix[4]- and resorcin[4]arene, are closely related, throughout the paper we use the name calix[4]arene-based (hemi)carcerands. We are aware that according to the definition of Cram et al. (ref. [7]) carcerands are synthetic organic compounds with enforced cavities large enough to complex complementary organic compounds or ions. Our hemicarcerands should be considered as potential hemicarcerands since unfortunately no complexation could be observed.
  • 33
    • 85036446540 scopus 로고    scopus 로고
    • note
    • It should be noted that due to the rigidity of the tetra-O-propylcalix[4]arene skeleton, 1,2-dinitro-mono-R-calix[4]arenes 2-5 are inherently chiral and, hence, exist as a mixture of two enantiomers.
  • 34
    • 85036439327 scopus 로고    scopus 로고
    • note
    • Beside the 1:1 coupled product two fractions of different 2:1 coupled products were isolated after preparative TLC in < 10% total yield. These products not only differ in the orientation of the calix[4]arene moiety with respect to the resorcin[4]arene moiety, that is, endo or exo, but also in the position of the phthalimido group on the calix[4]arene moieties, that is, cis or trans. Since these products were only formed in minor yields no further attempts were carried out to elucidate the exact nature of the products.
  • 35
    • 85036443299 scopus 로고    scopus 로고
    • note
    • The measurements were carried out at room temperature. Therefore, the observed structural properties correspond to those at room temperature and not at lower temperature.
  • 36
    • 85036444119 scopus 로고    scopus 로고
    • note
    • Since it is not possible to accurately determine distances with ROESY spectroscopy, the ratios of ROE build-up signals were determined. In a perfect cone conformation the ratios between the different distances will be 1, whereas in a pinched cone the ratios will be 1.1-1.2. For hemicarcerand 11 the ratios were 1.06 and 1.12.
  • 37
    • 85036443256 scopus 로고    scopus 로고
    • note
    • 1H NMR spectra below δ = 0 that are characteristic for incarcerated guests. Furthermore, no indications were found for the inclusion of methane after bubbling a solution of hemicarcerand with methane gas. Refluxing in toluene or THF and heating in DMA or N-ethyl-2-pyrrolidinone did not result in any carceplex. Hemicarcerand 12, bearing an extra O-propyl group, did not show the formation of a hemicarceplex after being heated in diphenyl ether/N-methyl-piperidone for 17 h. Inspection of CPK. molecular models as well as molecular modeling calculations indicate that all potential guests fit into the cavity of the hemicarcerand.
  • 39
    • 85036445788 scopus 로고    scopus 로고
    • note
    • The z-axis is defined as the axis that connects the centers of the calix[4]- and resorcin[4]arene moieties.
  • 43
    • 85036446914 scopus 로고    scopus 로고
    • note
    • The influence of the concentration of a potential guest during the doped inclusion experiments was investigated by carrying out experiments at 2, 5, 10, and 15 vol% guest. However, no significant differences in yield of the 2-butanone carceplex 22 were observed.
  • 45
    • 0004018410 scopus 로고
    • VCH, Weinheim
    • N is a normalized solvent parameter based on the transition energy for the longest wavelength absorption of pyridinium-N-phenoxide betaine dye, and is sensitive to dipolar interactions and hydrogen bonding. See: C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, 2nd ed., VCH, Weinheim, 1988, p. 408.
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    • Reichardt, C.1
  • 46
    • 85036449458 scopus 로고    scopus 로고
    • note
    • IUPAC name 2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide.
  • 55
    • 85036447367 scopus 로고    scopus 로고
    • note
    • In most cases the measurements were carried out at low temperature (ca. - 55°C). Since no change in chemical shift was observed for the resonances of the incarcerated guests it seems reasonable to assume that the orientation determined at low temperature corresponds to that at room temperature.
  • 56
    • 85036450171 scopus 로고    scopus 로고
    • note
    • 1H NMR spectrum hampers the detection of other conformers. Only the structure at lower temperature was elucidated.
  • 66
    • 85036447288 scopus 로고    scopus 로고
    • note
    • 4 at 120°C for 8 h or after heating a solid sample at 200°C for 16 h.
  • 67
    • 85036441377 scopus 로고    scopus 로고
    • note
    • Destruction of the carcerand would also lead to an increase in total ion current, which was not observed.
  • 68
    • 85036445819 scopus 로고    scopus 로고
    • note
    • 2 could be detected in the FD mass spectrometry experiment; this is most likely due to the technique used.
  • 69
    • 85036442647 scopus 로고    scopus 로고
    • note
    • 2 and butadiene from carceplex 23 with differential scanning calorimetry failed.
  • 70
    • 85036443053 scopus 로고    scopus 로고
    • note
    • For each structure the average of the two diametrical distances was calculated.
  • 75
    • 0029747145 scopus 로고    scopus 로고
    • Very recently, a molecular modeling study of resorcin[4]arene-based (hemi)carceplexes was reported: K. N. Houk, K. Nakamura, C. Sheu, A. E. Keating, Science 1996, 273, 627.
    • (1996) Science , vol.273 , pp. 627
    • Houk, K.N.1    Nakamura, K.2    Sheu, C.3    Keating, A.E.4
  • 76
    • 85036441835 scopus 로고    scopus 로고
    • note
    • Guest volumes were calculated within QUANTA/CHARM as the solvent-accessible surface.
  • 77
    • 85036448332 scopus 로고    scopus 로고
    • private communication
    • W. P. van Hoorn, private communication.
    • Van Hoorn, W.P.1
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    • note
    • -1).
  • 79
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    • Thesis, University of Twente
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    • (1995)
    • Timmerman, P.1
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    • 85036448959 scopus 로고    scopus 로고
    • note
    • During the synthesis of 23 the temperature was kept below 70°C to prevent decomposition of the potential guest.
  • 83
    • 85036448374 scopus 로고    scopus 로고
    • Molecular Simulations Inc., Waltham, MA
    • QUANTA version 3.0: Molecular Simulations Inc., Waltham, MA.
    • QUANTA Version 3.0
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    • W. F. van Gunsteren, H. J. C. Berendsen, Angew. Chem. 1990, 102, 1020; Angew. Chem. Int. Ed. Engt. 1990, 29, 992.
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  • 87
    • 85036449163 scopus 로고    scopus 로고
    • note
    • An initial step size of 0.05 Å with a maximum of 0.15 Å was used.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.