Unusual orientation and reactivity of alkyl halides in water-soluble cavitands

Water-soluble deep cavitands with ionic peripheral groups take up hydrophobic guest compounds in D sub(2)O. Longer n-halides and alpha , omega -dihalides C sub(7)-C sub(11), are bound and NMR is used to deduce their arrangements within the cavitand. The guests tumble rapidly on the NMR timescale, bu...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2014-01, Vol.5 (11), p.4382-4387
Main Authors: Hooley, Richard J., Gavette, Jesse V., Mettry, Magi, Ajami, Dariush, Rebek, Julius
Format: Article
Language:English
Subjects:
Halides
Halogens
Hydrolysis
Hydroxyl groups
Nuclear magnetic resonance
Orientation
Solvents
Time
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Summary:Water-soluble deep cavitands with ionic peripheral groups take up hydrophobic guest compounds in D sub(2)O. Longer n-halides and alpha , omega -dihalides C sub(7)-C sub(11), are bound and NMR is used to deduce their arrangements within the cavitand. The guests tumble rapidly on the NMR timescale, but unexpectedly, the halogen atoms compete with CH sub(3) groups for the aromatic panels near the bottom of the cavitand. Even a thiol can be found in the depths of the cavitand but not hydroxyl groups: 1,12-dodecanediol folds in the space leaving the ends exposed to solvent. The hydrolysis of bound guests is accelerated when the halides are near the cavitand rim.
ISSN:2041-6520
2041-6539
DOI:10.1039/C4SC01316F