22900-44-3Relevant articles and documents
Chastrette,Chastrette
, p. 534 (1973)
Wiegers,Smith
, p. 1126,1130 (1978)
Synthesis of Calixfuran Macrocycles and Evidence for Gas-phase Ammonium Ion Complexation
Musau, Richard M.,Whiting, Andrew
, p. 2881 - 2888 (2007/10/02)
Furan and 2-hydroxymethylfuran reacted under Lewis acidic conditions to yield oligomeric furylmethane compounds 5 and 6.Difurylmethane 5 was also obtained via the reaction of 2-furyllithium with bromochloromethane or reaction with 2-furaldehyde, followed by in situ reduction of the resulting lithium alkoxide with sodium boranuide-trifluoroacetic acid mixture.The trimeric furan compound 6a could also be prepared from furyllithium by a similar route.Oligomers 5 and 6 were utilised for a subsequent Lewis acid-catalysed cyclisation to afford calixfurans, i.e. cyclic tetramer 2a, and small quantities of the cyclic pentamer 2b, hexamer 2c and octamer 2e.Traces of cyclic heptamer 2d could also be detected under certain conditions.Chemical ionisation mass spectrometry using ammonia gas demonstrates that the calixfurans and their acyclic precursors are capable of chelating hydrogen and ammonium ions in the gas phase.
Role of Metal Salts in the Synthesis of Furan-Ketone Condensation Macrocycles: An 'Apparent' Metal Template Effect
Healy, Maria de Sousa,Rest, Antony J.
, p. 973 - 982 (2007/10/02)
The acid-catalysed condensation of furan and acetone has been investigated by systematically varying the parameters of the reaction.The dramatic yield enhancement for macrocycles found on adding metal salts, and hitherto assumed to be due to a metal ion template effect, has now been demonstrated to result from pH effects.Optimisation of condensation reaction conditions has enabled a number of tetrameric furan-ketone macrocycles to be synthesized with improved yields and a tetrameric furan-cyclohaxanone macrocycle has been synthesized in a one-step reaction for the first time.Hexameric and octameric furan-acetone macrocycles have also been prepared.The tetrameric furan-ketone macrocycles show no binding interaction with any metal ion but the tetrameric tetrahydrofuran-acetone macrocycle binds strongly enough with LiClO4 to form an isolable 1:1 complex and gives very strongly perturbed 1H n.m.r. spectra in the cases of LiSCN and Ni(ClO4)2*6H2O.Increasing the number of donor sites, as in the hexameric furan-acetone and hexameric tetrahydrofuran-acetone macrocycle, did not lead to complexation of metal ions.