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研究生:楊麗蓁
研究生(外文):Li-Chen Yang
論文名稱(外文):Computational DFT Study of The 1,3-Dipolar Cycloaddition of (2,6-Difluoro-Phenyl)-Triazomethane to 1-Substituted-1,2,3-Triazole
指導教授:李錫隆李錫隆引用關係
指導教授(外文):Shyi-Long Lee
口試委員:史蘭尼胡景瀚王伯昌
口試委員(外文):Slanina ZdeněkChing-Han HuBo-cheng Wang
口試日期:2014-07-25
學位類別:碩士
校院名稱:國立中正大學
系所名稱:化學暨生物化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2014
畢業學年度:102
語文別:英文
論文頁數:83
外文關鍵詞:1,3-dipolar cycloaddition
相關次數:
  • 被引用被引用:0
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The reaction and mechanism of the (2,6-difluoro-phenyl)-triazomethane to 1-substituted-1,2,3-triazole by 1,3-dipolar cycloaddition (1,3-DC) in the gas phase and the solvent phase have been investigated using DFT methods. The substituted 1,2,3-triazoles can be synthesized using arylazide and 2-chloroacrylonitrile in two steps by the 1,3-dipolar cycloaddition reaction (1,3-DC) and dehydrohalogenation reaction. The 1,3-dipolar cycloaddition reaction is the rate-determining step with the ΔG≠ of 36.1 and 22.1 kcal/mol at the B3LYP/6-31+G(d,p) and M06-2X/6-31+G (d,p) levels, respectively. For the solvent effect, solvent phase calculations were carried out using different solvent, respectively, water (ɛ=78.36), ethanol (ɛ=24.85), dimethylformamide (ɛ=37.22), toluene (ɛ=2.37), and n-heptane (ɛ=1.91) as the solvent in polarizable continuum model (PCM). And the results of PCM show that the energy barriers are proportional to solvents’ dielectric constants, which was disagreement with experimental observations. Further, the microsolvation was carried out using the water and ethanol as a solvent system at M06-2X/6-31+G (d,p) level. These computational results are in good agreement with the experimental observations. The aromatic azide (dipole) reacts with different alkenes (dipolarophile) such as nitrile, carboxylic acid, nitro, and amine groups. The results of HOMO-LUMO energy gap describes that the dipole reacts with different substituents of dipolarphile. The FMO gap between HOMO of R and LUMO of R- nitro is 3.90eV. The lowest band gap for nitro group among the different substituents shows that the reaction favors when the EWGs presents on the dipolarophile.
Abstract I
中文摘要 III
Scheme V
Table VI
Figure VII
Chapter 1 Introduction 1
Chapter 2 Computational Methods and Theoretical Backgrounds 4
2.1 Computational Methods in Detail 4
2.2 Density functional Theory (DFT) 7
2.2.1 B3LYP (Becke, three-parameter, Lee-Yang-Parr) 9
2.2.2 M06-2X 10
2.3 Basis Functions 13
2.3.1 Split-valence basis set 14
2.3.2 Polarization function 15
2.3.3 Diffuse function 15
2.4 Solvation 16
2.4.1 Self-consistent Reaction Field (SCRF) 16
2.4.2 Polarized Continuum Model (PCM) 17
2.4.3 The Microsolvation model (Explicit Solvation model) 19
Chapter 3 Results and Discussions 20
3.1 Mechanisms and Structure 20
3.2 Potential Energy Surface 25
3.3 Solvent effects 28
3.3.1 PCM 28
3.3.2 Microsolvation model 33
3.4 Substituents Effects 66
Chapter 4 Conclusions 74
Reference 77
Appendix 81
1,3-Dipolar Cycloaddition (1,3-DC) 81

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