Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 2, Pages 479-482Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201306673
Keywords
alcohol dehydration; heterogeneous catalysis; NMR spectroscopy; reaction mechanisms; zeolites
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Funding
- U. S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences Biosciences
- DOE by Battelle Memorial Institute [DE-AC06-76L0-1830]
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A microautoclave magic angle spinning NMR rotor is developed enabling insitu monitoring of solid-liquid-gas reactions at high temperatures and pressures. It is used in a kinetic and mechanistic study of the reactions of cyclohexanol on zeolite HBEA in 130 degrees C water. The (13)Cspectra show that dehydration of 1-C-13-cyclohexanol occurs with significant migration of the hydroxy group in cyclohexanol and the double bond in cyclohexene with respect to the C-13 label. A simplified kinetic model shows the E1-type elimination fully accounts for the initial rates of 1-C-13-cyclohexanol disappearance and the appearance of the differently labeled products, thus suggesting that the cyclohexyl cation undergoes a 1,2-hydride shift competitive with rehydration and deprotonation. Concurrent with the dehydration, trace amounts of dicyclohexyl ether are observed, and in approaching equilibrium, a secondary product, cyclohexyl-1-cyclohexene is formed. Compared to phosphoric acid, HBEA is shown to be a more active catalyst exhibiting a dehydration rate that is 100-fold faster per proton.
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