Synthesis of interstellar propen-2-ol (CH3C(OH)CH2) – the simplest enol tautomer of a ketone

Enols – tautomers of ketones or aldehydes – are anticipated to be ubiquitous in the interstellar medium and play a key role in the formation of complex organic molecules in deep space, but their fundamental formation mechanisms have remained largely elusive as of now. Here we present a combined experimental and computational study demonstrating the first preparation of propen-2-ol (CH3C(OH)CH2) and its isomer methyl vinyl ether (CH3OCHCH2) in low-temperature acetone (CH3COCH3) ices upon exposure to energetic electrons. Propen-2-ol is the simplest enol tautomer of a ketone. Exploiting tunable vacuum ultraviolet photoionization in conjunction with reflectron time-of-flight mass spectrometry, propen-2-ol and methyl vinyl ether were monitored in the gas phase upon sublimation during the temperature-programmed desorption process suggesting that both isomers are promising candidates for future astronomical searches such as via the James Webb Space Telescope. Electronic structure calculations reveal that the barrier of keto–enol tautomerization can be reduced by more than a factor of two (162 kJ mol−1) through the involvement of solvating water molecules under realistic conditions on interstellar grains. The implicit solvent effects, i.e., the influences of the solvent dipole field on the barrier height are found to be minimal and do not exceed 10 kJ mol−1. Our findings signify a crucial step toward a better understanding of the enolization of ketones in the interstellar medium thus constraining the molecular structures and complexity of molecules that form in extraterrestrial ices - ketones - through non-equilibrium chemistry.