在間質隔離系統下利用取代基效應、鹵素效應與TEMPO自由基捕獲來探討丙炔基衍生物與丙二烯基衍生物照光重組反應的反應機構

The mechanism study of the photo rearrangement of the substituted propargyl derivatives and allenyl derivatives in the matrix isolation by the substituent, the halogen effects and TEMPO radical trapping

廖家駒(Jia-Ju Liao)

指導教授 ： 吳裕文

義守大學/理工學院/化學工程學系暨生物技術與化學工程研究所/碩士(2015年)

https://doi.org/10.6343/ISU.2015.00246

摘要

在間質隔離系統下利用取代基效應與鹵素效應探討丙炔基衍生物與丙二烯基衍生物之照光重組反應，並討論其反應機構。

　　利用TEMPO捕捉自由基的方法來探討丙炔基衍生物與丙二烯基衍生物之照光重組反應所產生之自由基，發現TEMPO捕捉照光重組反應所產生之自由基的速率大於照光重組反應所產生之自由基的共振速率。

　　不同濃度的丙炔基溴甲苯溶液進行照光反應，發現可以嘗試利用動力學控制與熱力學控制來討論以化學方法來研究C3H3自由基得到的產物以丙炔基衍生物為主，而在間質隔離系統下卻有相當多量的丙二烯基衍生物生成。

關鍵字

丙炔基衍生物 ； 丙二烯衍生物 ； 動力學控制 ； 熱力學控制

並列摘要

To investigate the photo rearrangement reactions of the substituted propargyl derivatives and allenyl derivatives in matrix isolation by the substituent and halogen effects. The mechanism of the photorearrangement reactions was discussed.

To use the TEMPO trapping method to capture the radical generated from the photorearrangement reaction of the propargyl derivative and allenyl derivative. The results show that the rate of TEMPO traps C3H3 radical generated from the photorearrangement reaction of the propargyl derivative and allenyl is faster than the rate of resonance for C3H3 radical.

The results of photolytic reactions of propargyl bromide in toluene solution with different concentrations might be ascribed to the kinetic control reactions. However, the results of photolytic reactions of the substituted propargyl derivatives and allenyl derivatives in matrix isolation might be ascribed to thermodynamically control reactions partly.

並列關鍵字

propargyl derivative ； allenyl derivative ； kinetic control ； thermodynamically control

參考文獻

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