Synchrotron Photoionization Study of Furan and 2-Methylfuran Reactions with Methylidyne Radical (CH) at 298 K.
Synchrotron Photoionization Study of Furan and 2-Methylfuran Reactions with Methylidyne Radical (CH) at 298 K.
复制标题
298 K 下呋喃和 2-甲基呋喃与亚甲基自由基 (CH) 反应的同步加速器光电离研究。
DOI：
10.1021/acs.jpca.7b10382
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
G. Meloni
中科院分区：
文献类型：
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作者：
E. Carrasco;K. Smith;G. Meloni
利用美国劳伦斯伯克利国家实验室的同步辐射光源，在298 K下研究了呋喃和2-甲基呋喃与次甲基CH（X2）自由基的反应.反应产物通过多重光电离质谱观察，并根据其光电离光谱和动力学时间轨迹进行表征。在呋喃+ CH中观察到的主要产物是2，4-环己烯-1-酮（m/z = 80）、2-戊烯-4-炔醛（m/z = 80）和乙烯基乙炔（m/z = 52）。从2-甲基呋喃+ CH，2-4-环己烯-1-甲醛（m/z = 94），2，3，4-己三烯醛（m/z = 94），1，3-环戊二烯（m/z = 66），3-戊烯-1-炔（Z）（m/z = 66）和乙烯基乙炔（m/z = 52）是观察到的主要产物。利用势能表面扫描，提出了热力学有利的反应途径。CH加成到呋喃和2-甲基呋喃环中的π-键被发现是导致所有鉴定的初级产物形成的入口通道。两种反应都遵循H损失和CHO损失的模式，以及环状和非环状异构体的形成。
The reactions of furan and 2-methylfuran with methylidyne CH (X2Π) radical were investigated at 298 K using synchrotron radiation produced at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Reaction products were observed by multiplexed photoionization mass spectrometry and characterized based on their photoionization spectra and kinetic time traces. Primary products observed in furan + CH are 2,4-cyclopentadien-1-one (m/z = 80), 2-penten-4-ynal (m/z = 80), and vinylacetylene (m/z = 52). From 2-methylfuran + CH, 2-4-cyclopentadien-1-carbaldehyde (m/z = 94), 2,3,4-hexatrienal (m/z = 94), 1,3 cyclopentadiene (m/z = 66), 3-penten-1-yne (Z) (m/z = 66), and vinylacetylene (m/z = 52) are the primary products observed. Using potential energy surface scans, thermodynamically favorable reaction pathways are proposed. CH addition to the π-bonds in furan and 2-methylfuran rings was found to be the entrance channel that led to formation of all identified primary products. Both reactions follow patterns of H loss and CHO loss, as well as formation of cyclic and acyclic isomers.