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note
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The solvent seems to play a decisive role in the exclusive formation of the cyclic products, a finding which still waits for a genuine explanation. First experiments to identify and investigate the factors influencing the cyclization reaction of dialdehydes and diamines are underway. Preliminary results show that the solvent and the structure of the aldehyde and amine are the two main factors influencing the product distribution. More detailed results will be published elsewhere.
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12
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0037931222
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note
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Thus, new higher cycles are easily accessible. However, the sensitivity of the imine bond resulted in the re-formation of the thermodynamic mixture equilibrium after separation of the cycles. This problem is not existing when the corresponding amine macrocycles were used.
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13
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33751554242
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For similar results on cycle 3a cf.: R. Menif, A. E. Martell, P. J. Squattrito, and A. Clearfield, Inorg. Chem., 1990, 29, 4723.
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Clearfield, A.4
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14
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85085717913
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note
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1H-NMR spectrum indicates the dominance of 3d' in solution. Complexation experiments, however, give only complexes of 3d (cf. ref. 7).
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15
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37049092836
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Ch. T. Seto, J. P. Mathias, and G. M. Whitesides, J. Amer. Chem. Soc., 1993, 115, 1321.
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0346348185
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1H-NMR experiment we obtained spectra with unresolved signal patterns. Additional peaks correspond most probably to imine E/Z isomers of the imine substructures as known in literature [a] J. R. Pliego, A. F. C. Alcântara, D. P. Veloso, and W. B. Almeida, J. Braz. Chem. Soc., 1999, 10, 381.
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b) J. BjØrgo, D. R. Boyd, Ch. G. Watson, W. B. Jennings, and D. M. Jerina, J. Chem. Soc., Perkin Trans. 2, 1974, 1081]. As the imine macrocycles contain 4 or more imine bonds, different isomers occur, which make it impossible to determine coupling constants etc. This argumentation is supported by the fact that in case of reduced macrocycles (4a,b) nicely resolved spectra are obtained.
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