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.
Phys Chem Chem Phys
; 25(2): 936-953, 2023 Jan 04.
Article
em En
| MEDLINE
| ID: mdl-36285574
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.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Acetona
/
Acetatos
Tipo de estudo:
Prognostic_studies
Idioma:
En
Ano de publicação:
2023
Tipo de documento:
Article