Using FTIR/Matrix Isolation and Theoretical Calculation to Study the Reactions of Alkene Halides with Ozone and Oxygen

• Main Authors: Ting-Zhong Liao, 廖挺眾
• Other Authors: Mei-Lee Hwang
• Format: Others
• Language: zh-TW
• Published: 2008
• Online Access: http://ndltd.ncl.edu.tw/handle/96667928124320069841

碩士 === 義守大學 === 生物技術與化學工程研究所碩士班 === 96 === The reactions of ozone or oxygen with alkene halides (XHCCCl2, X=Cl, CH3) have been investigated by using matrix isolation/ FTIR, ab initio method and density functional theory. Applied the method of HF, MP2 and B3LYP levels at 6-311g** basis set to calculate the optimization of the geometric configurations and the energies of reactions, intermediates, transition states and products. Comparison of the calculated values with experimental results, suggested that the calculations with B3LYP level give better results.The reactions of alkene halides with oxygen have the product of tetracyclic compound in the experiment, and the intermediates are biradical carbonyl oxide from calculated results. The reaction of chloroacetylene with oxygen is similar to the reactions of alkene halides with oxygen, but the product of chloroacetylene with oxygen might decompose to form HClC(O) and carbon monoxide. Substituted electron withdrawing group on the double (or triple) bond of alkene halide or chloroacetylene will favor the reaction. The reaction of halogenated alkenes with oxygen form primary ozonide(POZ) first, then POZ decomposed to form intermediates, ABC(O) and XYCO2, which proceeds cycloaddition to form secondary ozonide(SOZ). The rate determining step of the reaction is the decomposition of primary ozonide. The intermediate XYCO2 is an electronic biradical therefore it is ready reacting when the substituent has an electron donating group. Electron donating substituted group on the carbon of double bond will favor the formation of π－complex to POZ.