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研究生:趙文芳
論文名稱:8,8-Dicyano,8,8-bis(Methoxycarbonyl)heptafulvenes與8,8-Diphenylbenzofulvene和6-Nonylfulvene之分子間[m+n]環化加成反應與反應機構研究
論文名稱(外文):Mecganisti Studies of Intermoleccular [m+n] Cycloaddition Reations of 8, 8-Dicyano-, 8, 8-bis-(Methoxycarbonyl)heptafulvenes with 8, 8-Diphenyl-benzofulvene and 6-Nonylfulvene
指導教授:劉清揚劉清揚引用關係
學位類別:碩士
校院名稱:文化大學
系所名稱:應用化學研究所
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:1994
畢業學年度:82
語文別:中文
論文頁數:80
中文關鍵詞:親電子性對稱雙取代基親核性對稱雙取代基
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親電子性對稱雙取代基之8,8-dicyanoheptafulvene(1a)和親核性對稱取代基之8,8-diphenylbenzoulvene(S1)於l80℃放入封管中,以xylene為溶劑,得到[4+2]anti,endo(C1);anti,exo(C2);syn,endo(C4);syn,exo(C5)四種環化加成生成物,除此之外,亦得到經由[1,5]氫轉移而形成熱穩定之[8+2]anti,endo(C3)環化加成生成物。當在140℃以xylene迴流及80℃以benzene迴流時,均得到上述相同生成物,但環化加成生成物間之比例互有改變。
將1a與親核性對稱取代基之6-nonylfulvene(S2)於140℃以xylene為溶劑,進行反應迴流時,得到[4+2]anti,endo(C6,C7)二種不同位向環化加成生成物及不可分離之syn,endo(C8,C9)二種不同位向環化加成生成物。於室溫攪拌下,可得不可分離之[8+2]anti,endo(C10,Cll)二種不同位向環化加成生成物;其餘尚有許多由於極性過於相近,故而無法由管柱色層分析法分離進而鑑定之未知生成物。
將較弱親電子性對稱雙取代基之8,8-biS(Methoxycarbonyl)-heptafulvene(1a)和S1進行環化加成反應,只在xylene中迥流反應時,才有一些生成物產生,但卻難以分離與鑑定。
當1b和S2進行環化加成反應時,由於光譜上氫與氫之訊號相互干擾重疊,或是環化加成生成物間之極性過於相近,故而無法由光譜上判定是否為欲求之環化加成生成物。


The cycloaddition reactions of electrondeficient 8,8-dicyanoheptafulvene(1a) with electron rich symmetrical 8,8-diphenylbenzofulvene(S1) thermolysis in xylene at 180℃ in a sealed tube. Give [4+2] anti, endo(C1); and, exo(C2); syn, endo(C4); syn, exo(C5) four cycloadducts and give [8+2] anti, eiido(C3) adduct, C3 under went 1,5-sigmatropic hydrogen shift to yield the thermodynamically more stable cyclopentadiene. When the reaction was carried out in refluxing xylene or benzene the result are still the same. But the yield between those cycloadducts are different.
The reaction of 1a with election rich unsymmetrical 6-nonylfulvene(S2). When the reaction was carried out in refluxing xylene, give [4+2] anti, endo regioisomers (C6, C7) and [4+2] syn, endo regioisomers(C8, C9) as an inseparable mixture. When the reaction was carried out at room temperature, give [8+2] anti, endo regioisomers (C10, C11) as an inseparable mixture. Except above, some adducts as an undentified adducts.
When the weaker electron-deficient 8,8-bis(methoxycarbonyl) heptafulvene (1b) was reacted with the (S1) in resulted information of some adducts as an inseparable mixture.
When(1b) was reated with the S2 in refluxing xylene or chloro form, according to some singals in spectrum are overlap too much and some of them as an inseparable mixture. So we cann't judge these adducts.

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