Mechanistical study on the formation of hydroxyacetone (CH3COCH2OH), methyl acetate (CH3COOCH3), and 3-hydroxypropanal (HCOCH2CH2OH) along with their enol tautomers (prop-1-ene-1,2-diol (CH3C(OH)CHOH), prop-2-ene-1,2-diol (CH2C(OH)CH2OH), 1-methoxyethen-1-ol (CH3OC(OH)CH2) and prop-1-ene-1,3-diol (HOCH2CHCHOH)) in interstellar ice analogs

Abstract

We unravel, for the very first time, the formation pathways of hydroxyacetone (CH₃COCH₂OH), methyl acetate (CH₃COOCH₃), and 3-hydroxypropanal (HCOCH₂CH₂OH), as well as their enol tautomers within mixed ices of methanol (CH₃OH) and acetaldehyde (CH₃CHO) analogous to interstellar ices in the ISM exposed to ionizing radiation at ultralow temperatures of 5 K. Exploiting photoionization reflectron time-of-flight mass spectrometry (PI-ReToF-MS) and isotopically labeled ices, the reaction products were selectively photoionized allowing for isomer discrimination during the temperature-programmed desorption phase. Based on the distinct mass-to-charge ratios and ionization energies of the identified species, we reveal the formation pathways of hydroxyacetone (CH₃COCH₂OH), methyl acetate (CH₃COOCH₃), and 3-hydroxypropanal (HCOCH₂CH₂OH) via radical–radical recombination reactions and of their enol tautomers (prop-1-ene-1,2-diol (CH₃C(OH)CHOH), prop-2-ene-1,2-diol (CH₂C(OH)CH₂OH), 1-methoxyethen-1-ol (CH₃OC(OH)CH₂) and prop-1-ene-1,3-diol (HOCH₂CHCHOH)) via keto-enol tautomerization. To the best of our knowledge, 1-methoxyethen-1-ol (CH₃OC(OH)CH₂) and prop-1-ene-1,3-diol (HOCH₂CHCHOH) are experimentally identified for the first time. Our findings help to constrain the formation mechanism of hydroxyacetone and methyl acetate detected within star-forming regions and suggest that the hitherto astronomically unobserved isomer 3-hydroxypropanal and its enol tautomers represent promising candidates for future astronomical searches. These enol tautomers may contribute to the molecular synthesis of biologically relevant molecules in deep space due to their nucleophilic character and high reactivity.