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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
Source PublicationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2011-07-20
DOI10.1021/ja2021476
Volume133Issue:28Pages:10864-10877
Indexed BySCI ; IC
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Multidisciplinary
WOS Research AreaChemistry
WOS KeywordHEXAMETHYL-DEWAR-BENZENE ; VALENCE-BOND ISOMERS ; DIELS-ALDER REACTION ; INTRAMOLECULAR CYCLOADDITIONS ; CATALYZED CYCLOTRIMERIZATION ; TRIMERIZATION REACTION ; TRANSITION STRUCTURES ; REACTION COORDINATE ; SINGLET DIRADICALS ; ADDITION-REACTIONS
AbstractTheoretical 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.
Language英语
WOS IDWOS:000293113200038
Citation statistics
Cited Times:24[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/142510
Collection中国科学院大连化学物理研究所
AffiliationPeking Univ, Beijing Natl Lab Mol Sci, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China
Recommended Citation
GB/T 7714
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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