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On the Mechanism of the Conversion of Methanol to 2,2,3-Trimethylbutane (Triptane) over Zinc Iodide

Bercaw, John E. and Diaconescu, Paula L. and Grubbs, Robert H. and Kay, Richard D. and Kitching, Sarah and Labinger, Jay A. and Li, Xingwei and Mehrkhodavandi, Parisa and Morris, George E. and Sunley, Glenn J. and Vagner, Patrick (2006) On the Mechanism of the Conversion of Methanol to 2,2,3-Trimethylbutane (Triptane) over Zinc Iodide. Journal of Organic Chemistry, 71 (23). pp. 8907-8917. ISSN 0022-3263. https://resolver.caltech.edu/CaltechAUTHORS:20170427-090114775

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Abstract

Methanol is converted to a mixture of hydrocarbons by reaction with zinc iodide at 200 °C with one highly branched alkane, 2,2,3-trimethylbutane (triptane), being obtained in surprisingly high selectivity. Mechanistic studies implicate a two-stage process, the first involving heterogeneously catalyzed formation of a carbon−carbon-bonded species, probably ethylene, that undergoes homogeneously catalyzed sequential cationic methylation to higher hydrocarbons. The first stage can be bypassed by addition of olefins, higher alcohols, or arenes, which act as initiators. Rationales for the particular activity of zinc iodide and for the selectivity to triptane are proposed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jo0617823DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jo0617823PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jo0617823PublisherSupporting Information
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Labinger, Jay A.0000-0002-1942-9232
Additional Information:© 2006 American Chemical Society. Received 29 August 2006. Published online 19 October 2006. Published in print 1 November 2006. Work at Caltech was supported by BP through the MC2 program. We thank Steve Cook, Gail Heath, and Matthew Deaves for assistance in performing some preliminary experiments on this system, Eugene Zaluzek for obtaining the PIANO analysis, and Philip Howard, Enrique Iglesia, Tom Knox, and Theo Fleisch for useful discussions.
Funders:
Funding AgencyGrant Number
BP MC2 ProgramUNSPECIFIED
Issue or Number:23
Record Number:CaltechAUTHORS:20170427-090114775
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170427-090114775
Official Citation:On the Mechanism of the Conversion of Methanol to 2,2,3-Trimethylbutane (Triptane) over Zinc Iodide John E. Bercaw, Paula L. Diaconescu, Robert H. Grubbs, Richard D. Kay, Sarah Kitching, Jay A. Labinger, Xingwei Li, Parisa Mehrkhodavandi, George E. Morris, Glenn J. Sunley, and Patrick Vagner The Journal of Organic Chemistry 2006 71 (23), 8907-8917 DOI: 10.1021/jo0617823
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76986
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:27 Apr 2017 16:16
Last Modified:03 Oct 2019 17:52

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