Hydrothermal Mineral-Assisted Organic Transformations of Carboxylic Acids

Tuesday, 16 December 2014
Kristin N Johnson, Ian Gould, Lynda B Williams, Hilairy Ellen Hartnett and Everett Shock, Arizona State University, Tempe, AZ, United States
The purpose of our research is to probe the varieties of reactions possible in a hydrothermal system in which both organic compounds and minerals interact. We performed experiments at physical conditions representative of deep-sea and subsurface systems (300°C and 1000 bar) and analyzed the effect of the mineral magnetite (Fe3O4) in systems with carboxylic acids, either phenylacetic acid or hydrocinnamic acid (a.k.a., phenylpropanoic acid). Control experiments were also conducted with the same organic compounds in the absence of magnetite. Whereas previous studies of carboxylic acid reactivity with minerals have focused exclusively on simple molecules such as acetic acid and valeric acid (Bell et al. 1994; McCollom et al. 2003), the carboxylic acids used in our study differ from previous experimental compounds by the addition of a phenyl ring, which allows for the investigation of the specific mechanistic pathways of product formation. Decarboxylation (i.e., RCO2H → RH + CO2) is one of the major reaction pathways for carboxylic acids in hydrothermal conditions without minerals. Under our experimental conditions, decarboxylation leads to the ~80% conversion of phenylacetic acid into toluene within ~50 hours and the ~8% conversion of hydrocinnamic acid to ethyl benzene within ~190 hours. We found that magnetite had a different effect on the two organic compounds studied. In experiments with phenylacetic acid, the presence of magnetite did not enhance the rate of toluene production from decarboxylation but did activate additional product pathways that include diphenyl alkanes, alkenes, and ketones, as well as benzoic acid, a carboxylic acid one carbon length shorter than the parent compound. Magnetite had even more noticeable effects on the hydrocinnamic acid system leading to an increase of its consumption at 190 hours from ~9% in magnetite’s absence to ~35% in the mineral’s presence. Products of the experiments with magnetite included an enhanced rate of decarboxylation product formation and activation of additional product pathways including diphenyl alkanes, alkenes, ketones and more. Our investigations involving reactivity of abundant functional groups, including carboxylic acids, reveal the varieties of processes available both on the Earth today and at the dawn of life.