Abstract

Alcohol dehydration by elimination of water is central to a series of functional group interconversions that have been proposed as a reaction pathway that connects hydrocarbons and carboxylic acids under geochemically relevant hydrothermal conditions, such as in sedimentary basins. Hydrothermal dehydration of alcohols is an example of an organic reaction that is quite different from the corresponding chemistry under ambient laboratory conditions. In hydrothermal dehydration, water acts as the solvent and provides the catalyst, and no additional reagents are required. This stands in contrast to the same reaction at ambient, where concentrated strong acids are required. Hydrothermal dehydration is thus of potential interest in the context of green chemistry. We have investigated the mechanism of hydrothermal alcohol dehydration for a series of secondary alcohols using studies of kinetics and stereoelectronic effects, in order to establish reaction mechanisms. The E1 elimination mechanism dominates over the corresponding E2 mechanism, with the E2 mechanism being competitive with E1 only for the most favorable stereoelectronically restricted alcohols included in the present study. These results are relevant to understanding the kinetics and product distributions of alcohol dehydration reactions in natural geologic systems, and can guide the development of organic chemical reactions that mimic geologic organic reactions under laboratory green chemistry conditions.

Original languageEnglish (US)
JournalACS Earth and Space Chemistry
DOIs
StateAccepted/In press - Mar 16 2018

Fingerprint

Dehydration
dehydration
alcohol
alcohols
Alcohols
kinetics
Kinetics
chemistry
elimination
Organic Chemicals
acids
Water
carboxylic acid
Hydrocarbons
Carboxylic Acids
carboxylic acids
chemical reaction
sedimentary basin
Functional groups
water

ASJC Scopus subject areas

  • Atmospheric Science
  • Geochemistry and Petrology
  • Space and Planetary Science

Cite this

Kinetics and Mechanisms of Dehydration of Secondary Alcohols under Hydrothermal Conditions. / Bockisch, Christiana; Lorance, Edward D.; Hartnett, Hilairy; Shock, Everett; Gould, Ian.

In: ACS Earth and Space Chemistry, 16.03.2018.

Research output: Contribution to journalArticle

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AU - Gould, Ian

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