UV-vis and IR spectral characterization of persistent carbenium ions, generated upon incorporation of cinnamyl alcohols in the acid zeolites HZSM-5 and HMor
Cinnamyl alcohol (1) and two derivatives 2 and 3 have been incorporated in dehydrated HMor and HZSM-5 zeolites with the aim to characterize spectroscopically the corresponding carbocations generated within the solids. Product studies of the supernatant liquid phase combined with diffuse reflectance UV-vis and IR spectroscopy provide unequivocal evidence for the carbocations. Thus, cinnamyl alcohol (1) affords the 1,5-diphenylpentadienyl cation in HMor and HZSM-5 as a persistent species. In the case of HMor with larger pore dimensions the bulkier 1-(2'-cinnamyl)-3-phenylpropenyl cation was also spectroscopically detected. No persistent carbocation was observed when the alpha-methylcinnamyl alcohol (2) was incorporated in the acid zeolites, wherein a complete cyclization to 2-methylindene takes place. Finally, incorporation of 2-methyl-4-tolyl-3-buten-2-ol (3) in HZSM-5 allowed detection of the gem-dimethyl-subsituted p-methylcinnamyl cation, with a lifetime of hours. This cation is not persistent enough in HMor to be characterized. The present study illustrates how structurally related allylic substrates may give distinct carbenium ions whose persistence depends on the host-guest fit in the interior of the acid zeolites.
Adam
W
Institute fur Organische Chemie, University of Wurzburg, Am Hubland, 97074 Wurzburg, Germany, and Instituto de Tecnologia Quimica CSIC-UPV, Universidad Politecnica de Valencia, Apartado 22012, 46071 Valencia, Spain.
Casades
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Fornes
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Garcia
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Weichold
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