13C CP/MAS and 2H NMR Study of tert-Butyl Alcohol Dehydration on H-ZSM-5 Zeolite. Evidence for the Formation of tert-Butyl Cation and tert-Butyl Silyl Ether Intermediates Full article
Journal |
Catalysis Letters
ISSN: 1011-372X , E-ISSN: 1572-879X |
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Output data | Year: 1992, Volume: 13, Number: 4, Pages: 407-422 Pages count : 16 DOI: 10.1007/BF00765044 | ||||
Tags | dehydration, H-ZSM-5 zeolite, mechanism of reaction, tert-butyl alcohol, tert-butyl cation, tert-butyl silyl ether | ||||
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Abstract:
The dehydration reaction of tert-butyl alcohol, selectively labelled with13C in CH3 or C-O groups (t-BuOH[2−13C2] and t−BuOH[1-13C]), as well as selectively deuterated in methyl groups (t-BuOH[2-2H9]), was studied on H-ZSM-5 zeolite simultaneously with 13-C CP/MAS and 2H solid state NMR. When adsorbed and dehydrated on zeolite at 296 K, t-BuOH[2−13C1] and t-BuOH[1−13C] give rise to identical 13C CP/MAS NMR spectra of oligomeric aliphatic products. This is explained in terms of the fast isomerization of the tert-butyl hydrocarbon skeleton via the formation of tert-butyl cation as the key reaction intermediate. An alkoxide species, most probably tert-butyl silyl ether (t-BuSE), was also detected as the “side” reaction intermediate. This intermediate was stable within the temperature range 296–373 K and decomposed at 448 K to produce additional amounts of final reaction products, i.e. butene oligomers. NMR data point to the existence of equilibria between the initial tert-butyl alcohol, tert-butyl cation and butene that is formed from the intermediate carbocation.
Cite:
Stepanov A.G.
, Zamaraev K.I.
, Thomas J.M.
13C CP/MAS and 2H NMR Study of tert-Butyl Alcohol Dehydration on H-ZSM-5 Zeolite. Evidence for the Formation of tert-Butyl Cation and tert-Butyl Silyl Ether Intermediates
Catalysis Letters. 1992. V.13. N4. P.407-422. DOI: 10.1007/BF00765044 WOS Scopus РИНЦ
13C CP/MAS and 2H NMR Study of tert-Butyl Alcohol Dehydration on H-ZSM-5 Zeolite. Evidence for the Formation of tert-Butyl Cation and tert-Butyl Silyl Ether Intermediates
Catalysis Letters. 1992. V.13. N4. P.407-422. DOI: 10.1007/BF00765044 WOS Scopus РИНЦ
Dates:
Submitted: | Feb 5, 1992 |
Accepted: | Mar 5, 1992 |
Published print: | Dec 1, 1992 |
Identifiers:
Web of science | WOS:A1992HV16500013 |
Scopus | 2-s2.0-0002400488 |
Elibrary | 30842159 |
Chemical Abstracts | 1992:511049 |
Chemical Abstracts (print) | 117:111049 |
OpenAlex | W2084891337 |