- 學位論文
（I）反應條件對一鍋式反應製備1-乙醯基-7-(3-氧代正丁基)-2,3,7-三氮-二環[3.3.0]辛-2-烯[1-acetyl-7-(3-oxo-butyl)-2,3,7-triaza-bicyclo[3.3.0]oct-2-ene]的影響 （II）利用TiCl4－Zn製備Pinacol
（I）The influences of reaction conditions on preparations of 1-acetyl-7-(3-oxo- butyl)-2,3,7-triaza-bicyclo[3.3.0]oct-2-ene （II）Preparation of pinacol using TiCl4－Zn
摘要
第一部分 本文主要是研究反應條件，對一鍋式反應製備2,3,7-三氮-二環[3.3.0]辛-2-烯類化合物的影響。在前人的方法中，直接一鍋式加入甲基乙烯基酮，得知有副產物4-疊氮基-丁-2-酮產生。但是在經過一系列研究後，發現副產物是由兩分子的甲基乙烯基酮進行[4＋2]環化加成，形成pyran。於是將溴化丙烯基與疊氮化鈉均勻反應12小時，以緩慢滴加方式加入甲基乙烯基酮，輔以核磁共振光譜的1H-nmr，的確在副產物問題上有顯著的改善。再利用改善條件，將溴化丙烯基置換成3-氯基-2-甲基-丙烯-[1]與丙烯酸甲酯，一鍋式合成出1-甲氧基羰基-5-甲基-7-(2-甲氧基羰基乙基)-2,3,7-三氮-二環[3.3.0]辛-3-烯，但此條件則不適合應用在甲基乙烯基酮以及丙烯氰上。除此之外，本文也進行丙烯酸甲酯在混合溶劑無水甲醇：丙酮=1：4下的反應，雖然可以一鍋式合成1-乙醯基-7-(3-氧代正丁基)-2,3,7-三氮-二環[3.3.0]辛-2-烯，但是與前人的核磁共振光譜1H-nmr比較，並沒有比較理想，無法符合一鍋式產物單純、分離簡單的原則，仍有改進的空間。 第二部分 本文主要是四氯化鈦－鋅對於製備pinacol的一系列研究。在前人的研究中，主要是利用四氯化鈦－鋅針對Wittig Reaction方面做研究。本文則將四氯化鈦、鋅粉以及溶劑四氫呋喃0℃攪拌一小時，再加入酮類，成功得到pinacol。
並列摘要
First part This thesis addresses on the influences of reaction conditions on preparations of 1-acetyl-7-(3-oxo- butyl)-2,3,7-triaza-bicyclo[3.3.0]oct-2-ene .In previous protocol ,directly adding methyl vinyl ketone for one pot reaction ,a residual side product was produced。After a series of study ,we found that the side product that was a dihydropyran from the [4＋2] cycloaddition of two molecules of methyl vinyl ketone .Thus by mixing allyl bromide and sodium azide and allowing the reaction to proceeds for 12 hours，then adding methyl vinyl ketone dropwise ,a remarkable improvement on the problem of the residual product was obtained .Then we utilize the improved conditions , replacing allyl bromide by 3-chloro-2-methyl propene ,to produce 1-methoxyl-5-methyl-7-(2-methoxylethylene)-2,3,7-triaza-bicyclo[3.3.0]oct-3-enes in one pot reaction .But these conditions were not suit methyl acrylate and acrylonitrile .Besides，This thesis also addresses on the reaction of methyl acrylate in a mixed solvents of methanol and acetone in 1：4 ratio .Although we can synthesis 1-acetyl-7-(3-oxo-butyl)-2,3,7-triaza-bicyclo[3.3.0]oct-2-ene in one pot reaction ,but we do not get a better result than previous protocol . Second part This thesis addresses on a series of study on the preparation of pinacol using TiCl4－Zn .In the past , principally utilize TiCl4－Zn to study about Wittig Reaction .Herein ,the mixture of TiCl4 and zinc powder in THF were stirred for 1 hour and then ketone was added to obtain pinacol .