臺灣博碩士論文加值系統

摘要
（壹）(E)-3-Phenyl-1-[(phenylsulfonyl)imino]-2-propene與甲基鋰試劑反應之機構探討
當(E)-3-Phenyl-1-[(phenylsulfonyl)imino]-2-propene (1) 與2當量MeLi反應，發現除了生成化合物2之外，也生成了其他的化合物3、4、5與6。證明出化合物3與6的反應機構。
化合物6的反應機構；Ph- 攻擊化合物1的C-4，進行1,4-加成反應，產生的負電荷間接攻擊接在SO2上的苯，進行環化反應形成六圓環結構，最後進一步氧化形成化合物6 。
化合物3是由化合物2與2當量的MeLi反應得來。2當量的MeLi先後拔除化合物2氮上的氫與接在SO2上苯的氫，產生N- 及Ph-，而Ph- 活性大於N- ，所以Ph- 直接攻擊在C-3上，進行環化反應，而形成六圓環的結構，所產生的負電荷可共振到苯上而被安定。經過work up的步驟，最後再斷掉C-N的鍵結而形成化合物3。
（貳）7-取代雙環[4.1.0]庚-1(7)-烯類化合物的合成與化性研究
當1,7,7-tribromo-bicyclo[4.1.0]heptane (36) 與2.5eq. MeLi反應後，會得化合物41與1,3-diphenylisobenzofuran(DPIBF)反應的化合物40。而化合物41的形成，證實是由化合物45與副產物MeBr反應而來。
化合物36與2.5eq. n-BuLi反應可形成化合物47。而化合物47是由化合物48開環而來。發現當一形成化合物34，會快速行ene-reaction而得化合物48，但化合物48會開環再與空氣中的O2反應而得化合物47。

Abstract
(1)
When (E)-3-phenyl-1-[(phenylsulfonyl)imino]-2-propene(1) was treated with 2 equivalent methyl lithium(MeLi),five compounds-2, 3, 4, 5, and 6 were isolated. The formation of products 3 and 6 were studied.
Compound 2 was treated with 2 equivalent MeLi to produce dianion 25.Dianion 25 underwent intramolecular reaction and reacted with water and deprotonation to generate anion 26 follwed by ring opening and proton absorption to form compound 3.
The formation of 6 is via carbanion exchange from methyl carbanion to phenyl carbanion. When compound 6 reacted with phenyl carbanion, the 1,4-addition adduct, carbanion was generated. Carbanion underwent intramolecular addition and proton absorption to provide compound 9 which was oxidized to form compound 6.
(2)
When 1,7,7-tribromo-bicyclo[4.1.0]heptane (36) was treated with 2.5 equivalent MeLi, generated intermediate 41 which was trapped with 1,3-diphenylisobenzofuran (DPIBF) to form compound 40..Intermediate 41 was proved by compound 45 react with side product MeBr.
Treatment of the compound 36 with 2.5 equivalent n-BuLi gave product 47 which is formed by intermediate 48 ring opening. We also found that compound 34 underwent ene-reaction fastly to give a dimeric product 48. But product 48 was unstabled to ring opening and reacted Oxygen in the air to give product 47.

目錄
中文摘要 ……………………………………………………………………………Ⅰ
英文摘要 ……………………………………………………………………………Ⅱ
（壹）(E)-3-Phenyl-1-[(phenylsulfonyl)imino]-2-propene與甲基鋰試劑反應之機構探討
一、緒論 ………………………………………………………………………………1
二、結果與討論 ………………………………………………………………………3
2-1. 起始物的合成 …………………………………………………………………..3
2-2. 反應機構的探討 ………………………………………………………………..3
三、結論 ……………………………………………………………………………..12
四、實驗部份 ……………………………………………………………………….13
五、參考文獻 ……………………………………………………………………….19
（貳） 7-取代雙環[4.1.0]庚-1(7)-烯類化合物的合成與化性研究
一、 緒論 ……………………………………………………………………………20
1-1. 前言 ……………………………………………………………………………20
1-2. 環丙烯的合成 …………………………………………………………………21
1-3. 1,3-融合雙環環丙烯類化合物之合成與反應 ………………………………..23
二、結果與討論 ……………………………………………………………………31
A. 1,7,7-Tribromo-bicyclo[4.1.0]heptane (36) 的合成 …………………………….31
B.7-Bromobicyclo[4.1.0]hept-1(7)-ene(39) 的合成 ……………………………….32
C.7-Subsituted bicyclo[4.1.0]hept-1(7)-enes 之製備 ……………………………...32
D.化合物36與excess的PhLi與PhS-反應 ………………………………………34
E. 化合物46的合成與excess的MeLi反應 ……………………………………..36
F. 化合物9與excess的MeLi反應 ………………………………………………39
G.化合物36與excess的n-BuLi反應 …………………………………………….41
三、結論 ……………………………………………………………………………..44
四、實驗部份 ……………………………………………………………………….45
五、參考文獻 ……………………………………………………………………….54
六、光譜數據 ……………………………………………………………………….57

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