臺灣博碩士論文加值系統

自由基加成至丙烯基化合物是進行自由基SH2''反應機構，利用3-氘-丙烯氯和3,3-二氘-丙烯氯的二級α-氘動力學同位素效應來決定SH2''反應其反應機構，3-氘-丙烯氯和3,3-二氘-丙烯氯的二級α-氘動力學同位素效應值分別測得0.89和0.78。在自由基SH2''反應中反向的(inverse) 動力學同位素效應值顯示自由基加成至雙鍵的步驟上是此反應的速率決定步驟，先前發表的1,1-二氘-丙烯氯的二級α-氘同位素效應值是1.22，說明SH2''反應中離去基的斷裂也是速率決定步驟。因此自由基SH2''反應被視為同步式反應機構而且3,3-二氘-丙烯氯與1,1-二氘-丙烯氯的同位素效應值接近指其過渡狀態是對稱性的。

The reactions of free radical addition to allylic compounds are believed to proceed the SH2'' mechanism. The secondary α-ducterium kinetic isotope effect of 3-d-allyl chloride and 3,3-d2-allyl chloride in free radical SH2'' reaction have been determined. The secondary α-ducterium kinetic isotope effects of 3,3-d2-allyl chloride and 3-d-allyl chloride were measured as 0.78 and 0.89 respectively. These inverse KIE indicate that the rate-determining-step is the radical addition to double bond in SH2'' reaction. The secondary α-ducterium of 1,1-d2-allyl chloride was reported as 1.22, therefore the breaking of leaving group was also indicate is the rate-determining-step. The free radical SH2'' reaction seem to favor the concerted mechanism and the value of the α-ducterium isotope effects of 3,3-d2-allyl chloride and 1,1-d2-allyl chloride are almost same, which indicates the transition state of SH2'' reaction is symmetrical.

中文摘要Ⅰ
英文摘要Ⅱ
誌謝Ⅲ
目錄Ⅳ
圖目錄Ⅵ
附圖目錄Ⅷ
表目錄Ⅸ
第一章 緒論1
第二章 實驗23
2-1 實驗藥品23
2-2 實驗儀器24
2-3 實驗方法25
2-3-1製備無水的四氫呋喃(THF)和乙醚(Ether)25
2-3-2 製備無水的二甲基甲醯胺(DMF)和二甲基亞碸(DMSO)25
2-3-3 製備3-氘-丙烯醇(3-d-allyl alcohol)26
2-3-4 製備3-氘-丙烯氯(3-d-allyl chloride)27
2-3-5 製備(Tert-Butyl Mercury Chloride)28
2-3-6 製備3-氘-丙炔醇(3-d-Propargy alcohol29
2-3-7 製備3,3-氘-丙烯醇(3,3-d-allyl alcohol31
2-3-8 製備3,3-氘-丙烯氯(3,3-d-allyl chloride)32
2-3-9 動力學測定方法33
2-3-10 GC實驗條件設定34
第三章 結果與討論35
3-1 汞化物個別和丙烯氯和2,3-二氯-1-丙烯進行照光反應35
3-2 丙烯氯和2,3-二氯-1-丙烯與汞化物進行照光競爭反應37
3-3 3-氘-丙烯氯和2,3-二氯-1-丙烯與汞化物進行照光競爭反應39
3-4 3,3-二氘-丙烯氯和2,3-二氯-1-丙烯與汞化物進行照光競爭反應40
3-5 二級α-氘同位素效應在自由基SH2''反應42
第四章 結論46
參考文獻47
附圖50

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