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20
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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.
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84989571860
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P. Timmerman, K. G. A. Nierop, E. A. Brinks, W. Verboom, F. C. J. M. van Veggel, W. P. van Hoorn, D. N. Reinhoudt, Chem. Eur. J. 1995, 1, 132.
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23
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0000378992
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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.
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24
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33748243226
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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.
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25
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37049077789
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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.
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-
26
-
-
85036448214
-
-
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.
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Pochini, A.7
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33
-
-
85036446540
-
-
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
-
-
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
-
-
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
-
-
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
-
-
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.
-
-
-
-
38
-
-
0029827165
-
-
For receptor molecules with extended hydrophobic surfaces see also: I. Higler, P. Timmerman, W. Verboom, D. N. Reinhoudt, J. Org. Chem. 1996, 61, 5920.
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39
-
-
85036445788
-
-
note
-
The z-axis is defined as the axis that connects the centers of the calix[4]- and resorcin[4]arene moieties.
-
-
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40
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0028259056
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a) R. G. Chapman, N. Chopra, E. D. Cochien, J. C. Sherman, J. Am. Chem. Soc. 1994, 116, 369;
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Chapman, R.G.1
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43
-
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85036446914
-
-
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
-
-
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
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46
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85036449458
-
-
note
-
IUPAC name 2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide.
-
-
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47
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0017816363
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84984180566
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B. S. Pedersen, S. Scheibye, N. H. Nilsson, S.-O. Lawesson, Bull. Soc. Chim. Belg. 1978, 87, 223.
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85036447367
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note
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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.
-
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56
-
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85036450171
-
-
note
-
1H NMR spectrum hampers the detection of other conformers. Only the structure at lower temperature was elucidated.
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85036447288
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-
note
-
4 at 120°C for 8 h or after heating a solid sample at 200°C for 16 h.
-
-
-
-
67
-
-
85036441377
-
-
note
-
Destruction of the carcerand would also lead to an increase in total ion current, which was not observed.
-
-
-
-
68
-
-
85036445819
-
-
note
-
2 could be detected in the FD mass spectrometry experiment; this is most likely due to the technique used.
-
-
-
-
69
-
-
85036442647
-
-
note
-
2 and butadiene from carceplex 23 with differential scanning calorimetry failed.
-
-
-
-
70
-
-
85036443053
-
-
note
-
For each structure the average of the two diametrical distances was calculated.
-
-
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72
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0000240789
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S. Fischer, P. D. J. Grootenhuis, L. C. Groenen, W. P. van Hoorn, F. C. J. M. van Veggel, D. N. Reinhoudt, M. Karplus, J. Am. Chem. Soc. 1995, 117, 1611.
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Van Veggel, F.C.J.M.1
Van Duynhoven, J.P.M.2
Harkema, S.3
Oude Wolbers, M.P.4
Reinhoudt, D.N.5
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75
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0029747145
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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.
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(1996)
Science
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Houk, K.N.1
Nakamura, K.2
Sheu, C.3
Keating, A.E.4
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76
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85036441835
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note
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Guest volumes were calculated within QUANTA/CHARM as the solvent-accessible surface.
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77
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85036448332
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private communication
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W. P. van Hoorn, private communication.
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Van Hoorn, W.P.1
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78
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85036440673
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note
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-1).
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79
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85036439634
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Thesis, University of Twente
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P. Timmerman, Thesis, 1995, University of Twente.
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(1995)
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Timmerman, P.1
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80
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85036448959
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note
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During the synthesis of 23 the temperature was kept below 70°C to prevent decomposition of the potential guest.
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-
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81
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0003412651
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Clarendon, Oxford
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R. R. Ernst, G. Bodenhausen, A. Wokaun, Principles of Nuclear Magnetic Resonance in One and Two Dimensions, Clarendon, Oxford, 1987.
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(1987)
Principles of Nuclear Magnetic Resonance in One and Two Dimensions
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Ernst, R.R.1
Bodenhausen, G.2
Wokaun, A.3
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83
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85036448374
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Molecular Simulations Inc., Waltham, MA
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QUANTA version 3.0: Molecular Simulations Inc., Waltham, MA.
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QUANTA Version 3.0
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84
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84986512474
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B. R. Brooks, R. E. Bruccoleri, B. D. Olafsen, D. J. States, S. Swaminathan, M. Karplus, J. Comput. Chem. 1983, 4, 187.
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(1983)
J. Comput. Chem.
, vol.4
, pp. 187
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Brooks, B.R.1
Bruccoleri, R.E.2
Olafsen, B.D.3
States, D.J.4
Swaminathan, S.5
Karplus, M.6
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85
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0000848422
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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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(1990)
Angew. Chem.
, vol.102
, pp. 1020
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Van Gunsteren, W.F.1
Berendsen, H.J.C.2
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86
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2142813682
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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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(1990)
Angew. Chem. Int. Ed. Engt.
, vol.29
, pp. 992
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87
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85036449163
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note
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An initial step size of 0.05 Å with a maximum of 0.15 Å was used.
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