| Summary: | 碩士 === 國立師範大學 === 化學學系 === 81 === (η-芳香烴)三羰錳陽離子錯合物早在1957年即被合成出來,以往,其它化
學家所利用的親核試劑多半無法攜帶官能基,由於,增加官能基可增加其
應 用性,故而,我們利用可攜帶官能基的有機鋅(鋅銅)試劑,來與(η-芳香
烴)三羰錳陽離子錯合物反應,並研究其應用性;首先,對芐基與烯丙基的有
機鋅試劑加成上,得到相當高的產率,但對長碳鏈帶有酯基與氰基的有機鋅
試劑產率並不理想,且從結果吾等有不尋常的發現,(1)作為溶劑的四氫夫
喃可在2位置與苯環加成,(2)親核試劑會重組,以官能基的α位置加成。本
篇論文的第二部份是利用C6+C6的方式,以實驗室發展的帶官能基有機鋅銅
試劑與(η-1,5-己二烯)三羰鐵陽離子錯合物行親核加成反應,合成含共軛
雙烯的費洛蒙,從而找出合理且便捷的合成應用方法。
It is well known that arenes complexed with
tricarbonylmanganese cations are actived toward nucleophilic
additions. for the first time, that allyl, benzyl as well as
functionalized zinc compounds are found to undergo these
additions. Reaction of (η-arene)tri- carbonylmanganese cation
with zinc-organometallics at 23 ℃ under a nitrogen atomsphere
produced neutral (η-cyclohexadienyl)tri- carbonylmanganese
complexes in good yield. Some unusual addition modes occure
when the organozinc reagents bear ester or cyano groups. (1)
the oxygen of THFcould coordinate to manganese and then the
proton of carbon 2 of solvent THF can be abstracted by
organozinc reagent yo add to (η-arene)tricarbonylmanganese
cat- ion by C-2 position. (2) the carbonyl or cyano groups of
organo- zinc reagents can coordinate to manganeses and then the
α proton of ester or cyano groups could be abstracted by the
organozinc reagents that can be added to (η-arene)
tricarbonylmanganes cat- ion by the α carbons of ester or
cyano groups. The addition reaction of organozinc copper
reagents with (η-1,5- hexadienyl)tricarbonyliron cation is
developed as a method for the synthesis for the preparation of
insect pheromones having con -jugated diene moiety.
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