The Gas-Phase Formation Mechanism of Dibenzofuran (DBF), Dibenzothiophene (DBT), and Carbazole (CA) from Benzofuran (BF), Benzothiophene (BT), and Indole (IN) with Cyclopentadienyl Radical
The Gas-Phase Formation Mechanism of Dibenzofuran (DBF), Dibenzothiophene (DBT), and Carbazole (CA) from Benzofuran (BF), Benzothiophene (BT), and Indole (IN) with Cyclopentadienyl Radical
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苯并呋喃 (BF)、苯并噻吩 (BT) 和吲哚 (IN) 与环戊二烯基自由基气相形成二苯并呋喃 (DBF)、二苯并噻吩 (DBT) 和咔唑 (CA) 的机理
DOI：
10.3390/ijms20215420
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发表时间：
2019-10
影响因子：
5.6
通讯作者：
Zhang Qingzhu
中科院分区：
文献类型：
--
作者：
Li Xuan;Gao Yixiang;Zuo Chenpeng;Zheng Siyuan;Xu Fei;Sun Yanhui;Zhang Qingzhu
Benzofuran (BF), benzothiophene (BT), indole (IN), dibenzofuran (DBF), dibenzothiophene (DBT), and carbazole (CA) are typical heterocyclic aromatic compounds (NSO-HETs), which can coexist with polycyclic aromatic hydrocarbons (PAHs) in combustion and pyrolysis conditions. In this work, quantum chemical calculations were carried out to investigate the formation of DBF, DBT, and CA from the reactions of BF, BT, and IN with a cyclopentadienyl radical (CPDyl) by using the hybrid density functional theory (DFT) at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants of crucial elementary steps were deduced over 600−1200 K, using canonical variational transition state theory with a small-curvature tunneling contribution (CVT/SCT). This paper showed that the production of DBF, DBT, and CA from the reactions of BF, BT, and IN with CPDyl involved six elementary steps: the addition reaction, ring closure, the first H shift, C–C cleavage, the second H shift, and elimination of CH3 or H. The cleavage of the C–C bond was regarded as the rate-determining step for each pathway due to the extremely high barrier. The 1-methyl substituted products were more easily formed than the 4-methyl substituted products. The main products were DBF and 1-methyl-DBF, DBT and 1-methyl-DBT, and CA and 1-methyl-CA for reactions of BF, BT, and IN with CPDyl, respectively. The ranking of DBF, DBT, and CA formation potential was as follows: DBT and methyl-DBT formation > DBF and methyl-DBF formation > CA, and methyl-CA formation. Comparison with the reaction of naphthalene with CPDyl indicated that the reactions of CPDyl attacking a benzene ring and a furan/thiophene/pyrrole ring could be inferred to be comparable under high temperature conditions.
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DOI：
10.1023/a:1023923409422
发表时间：
2003-06
期刊：
Water, Air, and Soil Pollution
影响因子：
--
作者：
B. Lim;Hong-Ying Hu;K. Fujie
通讯作者：
B. Lim;Hong-Ying Hu;K. Fujie
DOI：
10.1039/j19700001561
发表时间：
1970
期刊：
Journal of The Chemical Society A: Inorganic, Physical, Theoretical
影响因子：
--
作者：
R. Schaffrin;J. Trotter
通讯作者：
R. Schaffrin;J. Trotter
影响因子：
5.8
作者：
Soliman, Y. S.;Al Ansari, E. M. S.;Wade, T. L.
通讯作者：
Wade, T. L.
影响因子：
8.8
作者：
S. Meyer;H. Steinhart
通讯作者：
S. Meyer;H. Steinhart
影响因子：
2.6
作者：
Freitas, Vera L. S.;Gomes, Jose R. B.;Ribeiro da Silva, Maria D. M. C.
通讯作者：
Ribeiro da Silva, Maria D. M. C.