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题名: Mechanisms of the Thermal Cyclotrimerizations of Fluoro- and Chloroacetylenes: Density Functional Theory Investigation and Intermediate Trapping Experiments
作者: Yao, Zhong-Ke1;  Yu, Zhi-Xiang1
刊名: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
发表日期: 2011-07-20
DOI: 10.1021/ja2021476
卷: 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
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.
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
语种: 英语
WOS记录号: WOS:000293113200038
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142510
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Peking Univ, Beijing Natl Lab Mol Sci, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China

Recommended Citation:
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.
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