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Mechanisms of the Thermal Cyclotrimerizations of Fluoro- and Chloroacetylenes: Density Functional Theory Investigation and Intermediate Trapping Experiments
Yao, Zhong-Ke; Yu, Zhi-Xiang
刊名JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2011-07-20
DOI10.1021/ja2021476
133期:28页:10864-10877
收录类别SCI ; IC
文章类型Article
WOS标题词Science & Technology ; Physical Sciences
类目[WOS]Chemistry, Multidisciplinary
研究领域[WOS]Chemistry
关键词[WOS]HEXAMETHYL-DEWAR-BENZENE ; VALENCE-BOND ISOMERS ; DIELS-ALDER REACTION ; INTRAMOLECULAR CYCLOADDITIONS ; CATALYZED CYCLOTRIMERIZATION ; TRIMERIZATION REACTION ; TRANSITION STRUCTURES ; REACTION COORDINATE ; SINGLET DIRADICALS ; ADDITION-REACTIONS
英文摘要Theoretical studies of the mechanisms of the thermal cyclotrimerization of fluoro- and chloroacetylenes, which were reported by Viehe and Ballester, respectively, were conducted with the aid of density functional theory calculations of the (U)B3LYP functional, indicating that the thermal cyclotrimerizations of fluoro-and chloroacetylenes involve tandem processes of regioselectively stepwise [2+2] and stepwise [4+2] cycloadditions. These tandem processes generate 1,2,6-trihalo-Dewar benzenes and 1,2,4-trihalo-Dewar benzenes, which then isomerize to the corresponding benzenes when heated. The rate-determining step of the cyclotrimerizations of haloacetylenes is the dimerization step involving open-shell singlet diradical transition states and intermediates. The substituent effects in the thermal cyclotrimerization of haloacetylenes have been rationalized using frontier molecular orbital theory. The higher reactivity of fluoroacetylenes compared to that of chloroacetylenes is due to the fact that fluoroacetylenes have lower singlet triplet gaps than chloroacetylenes and more easily undergo dimerization and cyclotrimerization. In this report, additional experiments were performed to verify the theoretical prediction about the cyclotrimerization of chloroacetylene and to trap the proposed 1,4-dichlorocyclobutadiene intermediate. Experiments revealed that the thermal reaction of phenylchloroacetylene at 110 degrees C gave 1,2,3-triphenyltrichlorobenzene and 1,2,4-triphenyltrichlorobenzene together with a tetramer, cis-1,2,5,6-tetrachloro-3,4,7,8-tetraphenyltricyclo[4.2.0.0(2,5)]octa-3,7-diene. The proposed 1,4-diphenyldichlorocyclobutadiene intermediate in the thermal cyclotrimerization of phenylchloroacetylene was successfully trapped using dienophiles of maleic anhydride and dimethyl acetylenedicarboxylate.
语种英语
WOS记录号WOS:000293113200038
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被引频次:21[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/142510
专题中国科学院大连化学物理研究所
作者单位Peking Univ, Beijing Natl Lab Mol Sci, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China
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Yao, Zhong-Ke,Yu, Zhi-Xiang. Mechanisms of the Thermal Cyclotrimerizations of Fluoro- and Chloroacetylenes: Density Functional Theory Investigation and Intermediate Trapping Experiments[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2011,133(28):10864-10877.
APA Yao, Zhong-Ke,&Yu, Zhi-Xiang.(2011).Mechanisms of the Thermal Cyclotrimerizations of Fluoro- and Chloroacetylenes: Density Functional Theory Investigation and Intermediate Trapping Experiments.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,133(28),10864-10877.
MLA Yao, Zhong-Ke,et al."Mechanisms of the Thermal Cyclotrimerizations of Fluoro- and Chloroacetylenes: Density Functional Theory Investigation and Intermediate Trapping Experiments".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133.28(2011):10864-10877.
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