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標題: Research on General Synthesis of Polymer Intermediates Possessing 3-, 4-Isocarbostyril Groups
關鍵字: 雙胺酯;Isocarbostyril;單胺酯;二苯乙醛;苯乙烯胺酯;烯醇式;Enol Ether Form
出版社: 化學工程學系
在本論文發展出兩種方便製備 Isocarbostyrils 的合成方法。所採取之製備方法是以乙基胺酯(Ethyl Urethane)分別去和α-二苯乙酮(α-2-Phenyl Acetophenones)及 β-苯乙醛(β-phenyl Acetaldehydes)反應,製備出含有 α- 或 β-苯乙烯胺酯(α-,β-Styril Carbamates)的衍生物,作為 Isocarbostyrils 的前驅物。最後將 α- 或 β-苯乙烯胺酯在高溫反應條件下,進行 [1, 5] 分子內環化加成反應,分別可得到3- 或 4-isocarbostyrils。過程中會經過一個苯乙烯之異氰酸鹽(Styril isocyanate)之中間產物。
首先,我們發現可由 Darzen’s 合成法製得各種不同的二苯乙醛。這些二苯乙醛皆可在酸的催化下和 70~80 ℃ 減壓反應下,和乙基胺酯直接進行縮合反應。而一步製備出單胺酯(Monocarbamates)化合物。由此一步驟合成到β-苯乙烯胺酯的產率約85~90%。然後將 β-苯乙烯胺酯在苯基環己烷(Phenylcyclohexane)(bp=240 ℃)溶液中,經高溫反應下迴流 3 小時。由一步合成反應所得的 4-isocarbostyrils 不但有高達 75~85 %的產率,也縮短合成過程及實驗的時間。
在合成 3-isocarbostyril上,是以α-二苯乙酮為起始物,[這個起始物的合成可由 2-phenyl acetic acid chloride 和 苯經由 Friedel-Crafts 反應來製得],由於 α-二苯乙酮不會直接和乙基胺酯反應,所以此合成途徑是先經由酮類(Ketone)轉化成烯醇式(Enol Ether Form)之後,再與乙基胺酯反應。這個縮合的步驟通常必須在酸的催化及減壓反應(70~80 ℃)下,脫去醇類,如此便可進而得到 α-苯乙烯胺酯(α-Styril Carbamates)。最後苯乙烯胺酯在苯基環己烷(Phenylcyclohexane)(bp=240 ℃)溶液中,經高溫反應下迴流 3 小時,可得 3-isocarbostyril,且有一高的產率(78 %)。
這兩種通用性的合成途徑,可以製備出接有很多不同官能基的 Carbostyril 衍生物,我們可以利用此方法,在未來高分子中間體之設計及應用上。

In my research, two general methods of preparing isocarbostyrils have been developed. Raw materials for 3- and 4-isocarbostrils were phenyl acetaldehydes or phenyl benzylketones respectively, while urethane was used as the common reagent in both cases. In the first key step, styril monocarbametes were prepared via modified condensation steps to serve as the precursors. The final thermolysis of either α- or β-styril monocarbamates gave the final 3- or 4-isocarbosyrils respectively, through the styril isocyanate intermediates via an intermolecular 1,5-cyclization mechanism.
We found that different diphenyl acetaldehydes could be prepared individually and efficiently by Darzen’s Reactions using acetophenones as raw materials. The resulting diphenyl acetaldehydes could then undergo condensation with ethyl urethane directly at a temperature below 80℃ in formation of β-styril monocarbamates. The yields of this one-step synthesis of β-styril monocarbamates are in the ranges of 85 to 90 %. Thermolysis of β-styril monocarbametes was carried our in boiling phenylcyclo- hexane ( bp= 240 ℃) for 3 hours. These modifications shortened the overall steps for 4-isocarbostyirl synthesis while they enhanced the overall yields to the ranges of 75 to 85 %.
In the synthesis of 3-isocarbostyrils, phenyl benzylketones were utilized as our stating materials [They were synthesized by Friedel-Crafts Reaction of 2-phenyl acetic acid chloride and substituted benzenes.] 。Since phenyl benzylketones could not react with urethane directly, so the ketones were converted into their enol ether forms before treating with urethane. These condensation steps generally were carried out in the presence of acid catalyst under vacuum to remove the resulting alcohol for promoting complete conversions into α-styril monocarbamates. The conversion of α-styril monocarbamtes into 3-carbostyrils were also achieved in high yields ( 78%) using the similar thermolysis conditions in boiling phenylcyclohexane.
These two general synthetic schemes can serve as bases for preparing many functionalized carbostyrils needed for our future polymeric syntheses.
Appears in Collections:化學工程學系所

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