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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
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2022-10-17 , DOI: 10.1039/d2cp03543j Jia Wang 1, 2 , Joshua H Marks 1, 2 , Andrew M Turner 1, 2 , Anatoliy A Nikolayev 3, 4 , Valeriy Azyazov 3 , Alexander M Mebel 5 , Ralf I Kaiser 1, 2
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2022-10-17 , DOI: 10.1039/d2cp03543j Jia Wang 1, 2 , Joshua H Marks 1, 2 , Andrew M Turner 1, 2 , Anatoliy A Nikolayev 3, 4 , Valeriy Azyazov 3 , Alexander M Mebel 5 , Ralf I Kaiser 1, 2
Affiliation
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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.
中文翻译：
羟基丙酮 (CH3COCH2OH)、乙酸甲酯 (CH3COOCH3) 和 3-羟基丙醛 (HCOCH2CH2OH) 及其烯醇互变异构体 (prop-1-ene-1,2-diol (CH3C(OH)CHOH)、prop 的形成机理研究-2-ene-1,2-diol (CH2C(OH)CH2OH), 1-methoxyethen-1-ol (CH3OC(OH)CH2) and prop-1-ene-1,3-diol (HOCH2CHCHOH)) 在星际冰类似物
我们首次阐明了羟基丙酮 (CH 3 COCH 2 OH)、乙酸甲酯 (CH 3 COOCH 3 ) 和 3-羟基丙醛 (HCOCH 2 CH 2 OH) 及其烯醇互变异构体的形成途径甲醇 (CH 3 OH) 和乙醛 (CH 3CHO) 类似于 ISM 中的星际冰，在 5 K 的超低温下暴露于电离辐射。利用光电离反射飞行时间质谱 (PI-ReToF-MS) 和同位素标记的冰，反应产物被选择性光电离，从而允许程序升温脱附阶段的异构体鉴别。基于已鉴定物种的不同质荷比和电离能，我们揭示了羟基丙酮 (CH 3 COCH 2 OH)、乙酸甲酯 (CH 3 COOCH 3 ) 和 3-羟基丙醛 (HCOCH 2 CH ) 的形成途径2 OH）通过自由基-自由基重组反应及其烯醇互变异构体 (prop-1-ene-1,2-diol (CH 3 C(OH)CHOH), prop-2-ene-1,2-diol (CH 2 C(OH) CH 2 OH), 1-methoxyethen-1-ol (CH 3 OC(OH)CH 2 ) 和 prop-1-ene-1,3-diol (HOCH 2 CHCHOH))通过酮-烯醇互变异构化。据我们所知，1-methoxyethen-1-ol (CH 3 OC(OH)CH 2 ) 和 prop-1-ene-1,3-diol (HOCH 2CHCHOH)是首次通过实验鉴定。我们的研究结果有助于限制在恒星形成区域内检测到的羟基丙酮和乙酸甲酯的形成机制，并表明迄今为止在天文学上未观察到的异构体 3-羟基丙醛及其烯醇互变异构体是未来天文学研究的有希望的候选者。由于其亲核特性和高反应性，这些烯醇互变异构体可能有助于深空生物相关分子的分子合成。
更新日期：2022-10-17
中文翻译：
羟基丙酮 (CH3COCH2OH)、乙酸甲酯 (CH3COOCH3) 和 3-羟基丙醛 (HCOCH2CH2OH) 及其烯醇互变异构体 (prop-1-ene-1,2-diol (CH3C(OH)CHOH)、prop 的形成机理研究-2-ene-1,2-diol (CH2C(OH)CH2OH), 1-methoxyethen-1-ol (CH3OC(OH)CH2) and prop-1-ene-1,3-diol (HOCH2CHCHOH)) 在星际冰类似物
我们首次阐明了羟基丙酮 (CH 3 COCH 2 OH)、乙酸甲酯 (CH 3 COOCH 3 ) 和 3-羟基丙醛 (HCOCH 2 CH 2 OH) 及其烯醇互变异构体的形成途径甲醇 (CH 3 OH) 和乙醛 (CH 3CHO) 类似于 ISM 中的星际冰，在 5 K 的超低温下暴露于电离辐射。利用光电离反射飞行时间质谱 (PI-ReToF-MS) 和同位素标记的冰，反应产物被选择性光电离，从而允许程序升温脱附阶段的异构体鉴别。基于已鉴定物种的不同质荷比和电离能，我们揭示了羟基丙酮 (CH 3 COCH 2 OH)、乙酸甲酯 (CH 3 COOCH 3 ) 和 3-羟基丙醛 (HCOCH 2 CH ) 的形成途径2 OH）通过自由基-自由基重组反应及其烯醇互变异构体 (prop-1-ene-1,2-diol (CH 3 C(OH)CHOH), prop-2-ene-1,2-diol (CH 2 C(OH) CH 2 OH), 1-methoxyethen-1-ol (CH 3 OC(OH)CH 2 ) 和 prop-1-ene-1,3-diol (HOCH 2 CHCHOH))通过酮-烯醇互变异构化。据我们所知，1-methoxyethen-1-ol (CH 3 OC(OH)CH 2 ) 和 prop-1-ene-1,3-diol (HOCH 2CHCHOH)是首次通过实验鉴定。我们的研究结果有助于限制在恒星形成区域内检测到的羟基丙酮和乙酸甲酯的形成机制，并表明迄今为止在天文学上未观察到的异构体 3-羟基丙醛及其烯醇互变异构体是未来天文学研究的有希望的候选者。由于其亲核特性和高反应性，这些烯醇互变异构体可能有助于深空生物相关分子的分子合成。
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