Uncatalyzed, Regioselective Oxidation of Saturated Hydrocarbons in an Ambient Corona Discharge

Stephen T Ayrton; Rhys Jones; David S Douce; Mike R Morris; R Graham Cooks

doi:10.1002/anie.201711190

Uncatalyzed, Regioselective Oxidation of Saturated Hydrocarbons in an Ambient Corona Discharge

Angew Chem Int Ed Engl. 2018 Jan 15;57(3):769-773. doi: 10.1002/anie.201711190. Epub 2017 Dec 14.

Authors

Stephen T Ayrton¹, Rhys Jones², David S Douce², Mike R Morris², R Graham Cooks¹

Affiliations

¹ Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 47907, USA.
² MS Research, Waters Corporation, Wilmslow, UK.

PMID: 29193616
DOI: 10.1002/anie.201711190

Abstract

Atmospheric pressure chemical ionization (APCI) in air or in nitrogen with just traces of oxygen is shown to yield regioselective oxidation, dehydrogenation, and fragmentation of alkanes. Ozone is produced from ambient oxygen in situ and is responsible for the observed ion chemistry, which includes partial oxidation to ketones and C-C cleavage to give aldehydes. The mechanism of oxidation is explored and relationships between ionic species produced from individual alkanes are established. Unusually, dehydrogenation occurs by water loss. Competitive incorporation into the hydrocarbon chain of nitrogen versus oxygen as a mode of ionization is also demonstrated.

Keywords: hydrocarbons; mass spectrometry; nitrogen; oxidation; reaction mechanisms.

Publication types

Research Support, Non-U.S. Gov't