Kinetics and Mechanisms of Hydrothermal Dehydration of Cyclic 1,2- and 1,4-Diols

Christiana Bockisch, Edward D. Lorance, Hilairy E. Hartnett, Everett L. Shock, Ian R. Gould

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Hydrothermal dehydration is an attractive method for deoxygenation and upgrading of biofuels because it requires no reagents or catalysts other than superheated water. Although mono-alcohols cleanly deoxygenate via dehydration under many conditions, polyols such as those derived from saccharides and related structures are known to be recalcitrant with respect to dehydration. Here, we describe detailed mechanistic and kinetic studies of hydrothermal dehydration of 1,2- and 1,4-cyclohexanediols as model compounds to investigate how interactions between the hydroxyls can control the reaction. The diols generally dehydrate more slowly and have more complex reaction pathways than simple cyclohexanol. Although hydrogen bonding between hydroxyls is an important feature of the diol reactions, hydrogen bonding on its own does not explain the reduced reactivity. Rather, it is the way that hydrogen bonding influences the balance between the E1 and E2 elimination mechanisms. We also describe the reaction pathways and follow-up secondary reactions for the slower-dehydrating diols.

Original languageEnglish (US)
Pages (from-to)14299-14307
Number of pages9
JournalJournal of Organic Chemistry
Volume87
Issue number21
DOIs
StatePublished - Nov 4 2022

ASJC Scopus subject areas

  • Organic Chemistry

Fingerprint

Dive into the research topics of 'Kinetics and Mechanisms of Hydrothermal Dehydration of Cyclic 1,2- and 1,4-Diols'. Together they form a unique fingerprint.

Cite this