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Previous reports have referred to the product of the initial stage of Behrend's synthesis of CB[n, aq. HCl, 100°C, 3 equiv of formaldehyde as Behrend's polymer. The results reported in this paper suggest that this substance may, in fact, consist of a mixture of glycoluril oligomers, nor-seco-CB[n, and other kinetically controlled intermediates in the mechanism of CB[n] formation
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The influence of glycoluril concentration, acid identity and concentration and temperature have also been studied by Day and co-workers. The point in the mechanistic pathway where these variable exert their influence remains unclear
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In addition to oligomers 2-6, bis-ns-CB[10, ±-bis-ns-CB[6, and ns-CB[6] the crude reaction mixtures typically contain some CB[6] and CB[7, We have been unsuccessful in developing an HPLC method to more precisely quantify the components of the reaction mixture for several reasons including (1) incompatibility of silica gel with the aq acid required for solubility, 2) irreversible adsorption during Dowex ion-exchange chromatography, and (3) lack of a convenient chromophore for detection
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In addition to oligomers 2-6, bis-ns-CB[10], (±)-bis-ns-CB[6], and ns-CB[6] the crude reaction mixtures typically contain some CB[6] and CB[7]. We have been unsuccessful in developing an HPLC method to more precisely quantify the components of the reaction mixture for several reasons including (1) incompatibility of silica gel with the aq acid required for solubility, (2) irreversible adsorption during Dowex ion-exchange chromatography, and (3) lack of a convenient chromophore for detection.
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(b) Rowan, A. E.; Elemans, J. A. A. W.; Nolte, R. J. M. Acc. Chem. Res. 1999, 32, 995-1006.
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Rowan, A.E.1
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(c) Wu, A.; Chakraborty, A.; Fettinger, J. C.; Flowers, R. A., II.; Isaacs, L. Angew. Chem., Int. Ed. 2002, 41, 4028-4031.
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Wu, A.1
Chakraborty, A.2
Fettinger, J.C.3
Flowers II, R.A.4
Isaacs, L.5
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61
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(d) Isaacs, L.; Witt, D. Angew. Chem., Int. Ed. 2002, 41, 1905-1907.
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Isaacs, L.1
Witt, D.2
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The formation of CB[10]·CB[5] and the gelation of purified CB[7] provide evidence for the (self)-association of CB[n] in aqueous solution. Although the presented x-ray structure is a solid state structure we find it highly likely that glycoluril oligomers will also undergo (self)-association in aqueous solution.
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The formation of CB[10]·CB[5] and the gelation of purified CB[7] provide evidence for the (self)-association of CB[n] in aqueous solution. Although the presented x-ray structure is a solid state structure we find it highly likely that glycoluril oligomers will also undergo (self)-association in aqueous solution.
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Huang, W.-H.; Zavalij, P. Y.; Isaacs, L. Angew. Chem., Int. Ed. 2007, 46, 7425-7427.
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Angew. Chem., Int. Ed
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, pp. 7425-7427
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Huang, W.-H.1
Zavalij, P.Y.2
Isaacs, L.3
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Huang, W.-H.; Zavalij, P. Y.; Isaacs, L. Org. Lett. 2008, 10, 2577-2580.
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Huang, W.-H.1
Zavalij, P.Y.2
Isaacs, L.3
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65
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46049113458
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The isolation of 2-6, bis-ns-CB[10], (±)-bis-ns- CB[6], and ns-CB[6] from reaction mixtures containing a deficiency of formaldehyde was possible because this stoichiometric imbalance slows down their transformation to the thermodynamically more stable CB[n]. In particular, the precipitation of certain compounds (e.g. bis-ns-CB[10]) from the reaction mixture can result in significant kinetic stability.
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The isolation of 2-6, bis-ns-CB[10], (±)-bis-ns- CB[6], and ns-CB[6] from reaction mixtures containing a deficiency of formaldehyde was possible because this stoichiometric imbalance slows down their transformation to the thermodynamically more stable CB[n]. In particular, the precipitation of certain compounds (e.g. bis-ns-CB[10]) from the reaction mixture can result in significant kinetic stability.
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66
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Compounds 13(m,n) and 17(m,n) are chiral when m ≠ n.
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Compounds 13(m,n) and 17(m,n) are chiral when m ≠ n.
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1H NMR spectroscopy is challenging.
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1H NMR spectroscopy is challenging.
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68
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This analysis is theoretically based and ignores the potential influence of strain and intramolecular NH⋯O H-bonds that are known to impact the stability and geometry of CB[n] and (±)-bis-ns-CB[6
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This analysis is theoretically based and ignores the potential influence of strain and intramolecular NH⋯O H-bonds that are known to impact the stability and geometry of CB[n] and (±)-bis-ns-CB[6].
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69
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Blanch, R. J.; Sleeman, A. J.; White, T. J.; Arnold, A. P.; Day, A. I. Nano Lett. 2002, 2, 147-149.
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Blanch, R.J.1
Sleeman, A.J.2
White, T.J.3
Arnold, A.P.4
Day, A.I.5
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70
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In none of these reactions did we observe the formation of CB[10]·CB[5] which suggests that the formation of this aggregate is probably more complex than the reaction of two molecules of 5 to give CB[10] followed by stabilization with CB[5].
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In none of these reactions did we observe the formation of CB[10]·CB[5] which suggests that the formation of this aggregate is probably more complex than the reaction of two molecules of 5 to give CB[10] followed by stabilization with CB[5].
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71
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Day has previously shown that CB[n] forming reactions when conducted at high dilution lead mainly to CB[5]. At high dilution intermolecular reactions are slowed and chain-growth rather than step-growth processes tend to dominate.
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Day has previously shown that CB[n] forming reactions when conducted at high dilution lead mainly to CB[5]. At high dilution intermolecular reactions are slowed and chain-growth rather than step-growth processes tend to dominate.
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(a) Oh, K. S.; Yoon, J.; Kim, K. S. J. Phys. Chem. B 2001, 105, 9726-9731.
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Maslii, A.N.1
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