Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3387
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dc.contributor.advisor戴憲弘zh_TW
dc.contributor.advisorShenghong A. Daien_US
dc.contributor.authorCHEN, LI-YUEHen_US
dc.contributor.author陳麗月zh_TW
dc.date2005zh_TW
dc.date.accessioned2014-06-06T05:31:51Z-
dc.date.available2014-06-06T05:31:51Z-
dc.identifier.urihttp://hdl.handle.net/11455/3387-
dc.description.abstract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。zh_TW
dc.description.abstractIn 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.zh_TW
dc.description.tableofcontents目 錄 索 引 含 3-,4-Isocarbostyrils 團基之高分子中間體的一般合成方法及研究 頁次 致謝………….....................………..…………….………........................................ I 中文摘要……….....................………..……………..……………............................... II 英文摘要………….....................………..…….…………..……….........……..……. IV 目錄索引….....................………..……………...…….………….....…………..…….V 目錄……………………………………………………..............…………...…....…VII 圖目錄………….....................………..………………..........................................…IX Scheme………….....................…………...……………...............…………...……... XI 表目錄……....................………………..……..………...................…..………....…XII 附錄……....................………………..……..……………..................…………..…XIII 目 錄 含 α-,β-Isocarbostyrils 團基之高分子中間體的一般合成方法及研究 頁次 第一章 緒論 1-1 前言……………………….....................………..……………...………...…..…… 1 1-2 文獻回顧…………………………….....................………………………….......... 4 1-2-1 3-、4-Substituted Isocarbostyrils 合成之相關文獻……............................. 4 1-2-2 3-、4-Substituted Isocarbostyrils 應用之相關文獻................................... 13 第二章 研究動機及目標 2-1 研究動機................................................................................................................. 19 2-2 目標......................................................................................................................... 23 第三章 結果與討論 3-1 p,p'-Dibromobenzophenone 之合成探討............................................................... 24 3-2 p-、p,p-Substituted diphenylacetaldehyde 之製備流程........................................ 25 3-2-1 合成 Ethyl(diphenyl)glycidate 步驟 I 之探討......................................... 26 3-2-2 合成 Sodium(diphenyl)glycidate 步驟 II 之探討................................... 30 3-2-3 合成 Diphenylacetaldehyde 步驟 III 之探討.......................................... 31 3-3 4-Substituted Isocarbostyrils 之製備流程.......................................................... 32 3-3-1 合成 4-Isocarbostyril 步驟 I~III 之探討................................................. 33 3-3-2 二步合成 4-Isocarbostyril 步驟 IV 之探討............................................ 34 3-3-3 一步合成 4-Isocarbostyril 步驟 V 之探討.............................................. 45 3-4 4-Methylisocarbostyril 之探討............................................................................... 48 3-5 (2-Phenylethylidene)biscarbamate 之探討......................................................... 51 3-6 3-Substituted Isocarbostyrils 之製備流程.......................................................... 52 3-6-1 反應路徑 I 之探討..................................................................................... 52 3-6-3 反應路徑 II 之探討................................................................................... 55 3-6-4 反應路徑 III 之探討.................................................................................. 57 3-6-5 反應路徑 IV之探討................................................................................... 60 第四章 結論....................................................................................................................... 63 第五章 實驗部份 5-1 藥品......................................................................................................................... 66 5-2 溶劑 & 觸媒......................................................................................................... 70 5-3 其他......................................................................................................................... 72 5-4 儀器部分................................................................................................................. 72 5-5 實驗裝置................................................................................................................. 75 5-6 實驗步驟................................................................................................................. 76 5-6-1 Ethyl β,β-Di(p-chlorophenyl)glycidate 的合成 [3-2a] ............................. 76 5-6-2 Sodiumβ,β-Di(p-chlorophenyl)glycidate 的合成 [3-3a] .......................... 77 5-6-3 p,p-Dichlorodiphenylacetaldehyde 的合成 [3-4a] ................................... 78 5-6-4 Ethyl 2,2-bis(p-chlorophenylvinyl)biscarbamate 的合成 [3-5a] .............. 79 5-6-5 從 [3-4a] 直接一步合成 Ethyl 2,2-bis(p-chlorophenylvinyl)carbamate [3-6a]…………...………… 80 5-6-6 從 [3-6a] 合成 7-chloro-4-(p-chlorophenyl)Isocarbostyril [3-7a] ........... 82 5-6-7 從 [3-4a] 直接合成 7-chloro-4-(p-chlorophenyl)isocarbostyril [3-7a] ... 83 5-6-8 p,p-dibromobenzophenone 的合成 [3-1b] ................................................ 84 5-6-9 Ethyl β, β-Di(p-bromophenyl)glycidate 的合成 [3-2b] ............................ 86 5-6-10 從 [3-1b] 合成 Sodiumβ,β-Di(p-bromophenyl)glycidate [3-3b] ........... 87 5-6-11 p,p-Dibromodiphenylacetaldehyde 的合成 [3-4b] .................................. 89 5-6-12 從 [3-4b] 直接一步合成 Ethyl 2,2-bis(p-bromophenylvinyl)carbamate [3-6b] ................................ 90 5-6-13 從 [3-6b] 合成 7-bromo-4-(p-bromophenyl)Isocarbostyril [3-7b] ........ 91 5-6-14 從 [3-1c] 合成 Sodium β ,β-( p– nitrophenyl )glycidate [3-3c] ............. 93 5-6-15 p-Nitrodiphenylacetaldehyde 的合成 [3-4c] ........................................... 94 5-6-16 從 [3-4c] 合成 4-(p- Nitrophenyl)isocarbostyril [3-7c] .................... 95 5-6-17 從 [3-8] 直接一步合成 4-Methylisocarbstyril [3-11] ........................... 96 5-6-18 (2-phenylethylidene)biscarbamate [3-12] 的合成................................... .98 5-6-19 (cis),(trans)-1-Methoxyl-1,2-diphenylethene 的合成 [3-15a] ............... .99 5-6-20 Ethyl-(1,2-diphenylvinyl)Carbamate 的合成 [3-16] ............................ 100 5-6-21 從 [3-13] 直接一步合成 Ethyl-(1,2-diphenylvinyl)Carbamate [3-16] ........................................... 101 5-6-22 3-Phenylisocarbostyril 的合成 [3-17] ................................................... 102 圖 目 錄 含 3-,4-Isocarbostyrils 團基之高分子中間體的一般合成方法及研究 頁次 圖 1-1 共軛聚合物構造........................................................................................................... 3 圖 3-1 不同比例 [3-1a]:Potassium tert-Butyloxide 所得 [3-2a]-NMR........................... 28 圖 3-2 [3-2a~c] 化合物-IR..................................................................................................... 29 圖 3-3 [3-5a] 的化學結構式………………………………………………………………...35 圖 3-4 化合物 [3-5a] 過程監測-IR...................................................................................... 36 圖 3-5 化合物 [3-5a] 過程監測-NMR................................................................................. 36 圖 3-6 [3-6a] 的化學結構式.................................................................................................. 37 圖 3-7 化合物 [3-6a] 過程監測-IR...................................................................................... 38 圖 3-8 化合物 [3-6a] 過程監測-NMR................................................................................. 38 圖 3-9 化合物 [3-5b]、[3-6b] 過程監測-IR......................................................................... 40 圖 3-10 化合物 [3-5b]、[3-6b] 過程監測-NMR................................................................. 40 圖 3-11 化合物 [3-5b]、[3-6b] 的化學結構式.................................................................... 41 圖 3-12 化合物 [3-7a] 230 ℃ 過程監測-IR..................................................................... 42 圖 3-13 各溫度下化合物 [3-7a] -IR.................................................................................... 43 圖 3-14 各溫度下化合物 [3-7a] -NMR............................................................................... 43 圖 3-15 化合物 [3-7b] 230 ℃ 過程監測-IR.................................................................... 44 圖 3-16 化合物 [3-5a~c] 過程監測-IR................................................................................ 46 圖 3-17 化合物 [3-6a~c] 過程監測-IR................................................................................ 46 圖 3-18 產物 [3-7a~c] 230℃ 反應 4 小時後監測-IR.................................................... 47 圖 3-19 化合物 [3-9]、[3-10] 過程監測-IR........................................................................ 50 圖 3-20 產物 [3-11] 過程監測-IR........................................................................................ 50 圖 3-21 產物 [3-15] 過程監測-IR………………………………………………………… 55 圖 3-22 產物 [3-17] 220 ℃ 過程監測-IR........................................................................ 58 圖 3-23 產物 [3-17] 240 ℃ 過程監測-IR........................................................................ 58 圖 3-24 產物 [3-16] 過程監測-IR........................................................................................ 62 圖5-5-1 減壓蒸餾裝置圖....................................................................................................... 75 圖5-5-2 反應裝置(用於液相加熱裂解反應) ....................................................................... 75 Scheme 含 3-,4-Isocarbostyrils 團基之高分子中間體的一般合成方法及研究 頁次 Scheme 1-1 E. J. Moricoxi 等人合成 3-Alkylisocarbostyril 之程………............................. 4 Scheme 1-2 化合物 3-Alkylisocarbostyril 之反應機構……….............................................5 Scheme 1-3 化合物 3-Alkylisocarbostyril 之互變異構物………….................................... 6 Scheme 1-4 W. T. Boyce 和 R. Levine 合成 3-Substituted Isocarbostyrils 之反應機構及流程...................................................... 7 Scheme 1-5 高溫環化反應合成 3-Substituted isocarbostyri1s.............................................. 8 Scheme 1-6 光環化反應合成 4-Phenylisocarbostyril............................................................ 9 Scheme 1-7 B. F. Powell 等人合成 3-Phenylisocarbostyril 之程....................................... 10 Scheme 1-8 低溫方式合成 3-Substituted isocarbostyrils 之反應機構及流程................... 11 Scheme 1-9 經由單胺酯(Monocarbamates)化合物所合成之 3-Substituted isocarbostyrils 和 4-Substituted isocarbostyrils............................... 12 Scheme 1-10 W. J. Cho 等人和成 3-Substituted Isocarbostyrils 之流程............................ 17 Scheme 2-1 4-Substituted Isocarbostyrils 之製備流程...................................................... 20 Scheme 2-2 3-Substituted Isocarbostyrils 之製備流程.......................................................21 Scheme 2-3 含胺基的 Coumarin 化合物之分子內的電荷傳遞......................................... 22 Scheme 3-1 合成 p,p-Dibromobenzophenone [3-1b] 反應機構........................................... 24 Scheme 3-2 合成 Diphenylacetaldehyde 之流程..................................................................25 Scheme 3-3 化合物 [3-2a~c] 之合成及反應機構.............................................................. 29 Scheme 3-4 Scheme 3-4 化合物 [3-4a~c] 反應機構............................................................31 Scheme 3-5 合成4-Isocarbostyril 流程圖............................................................................. 32 Scheme 3-6 合成 4-Methylisocarbstyril [3-11] 之流程……………………………………48 Scheme 3-7 合成(2-phenylethylidene)biscarbamate [3-12] 之流程................................. 50 Scheme 3-8 以苯乙醛二甲縮醛合成(2-phenylethylidene)biscarbamate 之流程............... 51 Scheme 3-9 合成 3-Isocarbostyril 流程................................................................................ 52 Scheme 3-10 依勒沙特列原理表示產物 [3-15] 產率不高的原因……………….…........ 55 Scheme 3-11 整個 3-Isocarbostyril 反應機構......................................................................59 Scheme 3-12 一步合成到 Ethyl-(1,2-diphenylvinyl)Carbamate [3-16] 之反應機構…..…61 表 目 錄 頁次 Table 1-1 細胞毒殺活性測試.................................................................................................. 14 附 錄 含 α-,β-Isocarbostyrils 團基之高分子中間體的一般合成方法及研究 頁次 附錄一 Ethyl β,β-Di(p-chlorophenyl)glycidate [3-2a]....................................... 104 附錄二 Sodiumβ,β-Di(p-chlorophenyl)glycidate [3-3a].....................................105 附錄三 p,p-Dichlorodiphenylacetaldehyde [3-4a]............................................. 106 附錄四 Ethyl 2,2-bis(p-chlorophenylvinyl)biscarbamate [3-5a]......................... 107 附錄五 Ethyl 2,2-bis(p-chlorophenylvinyl)carbamate [3-6a]………………… 109 附錄六 7-Chloro-4-(p-chlorophenyl)Isocarbostyril [3-7a]................................. 111 附錄七 p,p-Dibromobenzophenone [3-1b]…….................................................. 114 附錄八 Ethyl β, β-Di(p-bromophenyl)glycidate [3-2b]....................................... 115 附錄九 Sodiumβ,β-Di(p-bromophenyl)glycidate [3-3b]…................................ 116 附錄十 p,p-Dibromodiphenylacetaldehyde [3-4b].............................................. 117 附錄十一 Ethyl 2,2-bis(p-bromophenylvinyl)carbamate [3-6b]......................... 118 附錄十二 7-Bromo-4-(p-bromophenyl)Isocarbostyril [3-7b]............................ 120 附錄十三 Sodium β ,β-( p– nitrophenyl )glycidate [3-3c].................................. 123 附錄十四 p-Nitrodiphenylacetaldehyde [3-4c]................................................... 124 附錄十五 7-(p- Nitrophenyl)isocarbostyril [3-7c]......................................... 125 附錄十六 4-Methylisocarbostyril [3-11]........................................................... 126 附錄十七 (2-phenylethylidene)biscarbamate [3-12]........................................... 128 附錄十八 (cis),(trans)-1–Methoxyl–1,2-diphenylethene [3-15]…..................... 129 附錄十九 (trans)-1–Methoxyl–1,2-diphenylethene [3-15].................................. 130 附錄二十 Ethyl-(1,2-diphenylvinyl)Carbamate [3-16]...................................... 132 附錄二十一 3-Phenylisocarbostyril [3-17]........................................................ 134 附錄二十二 細胞計數與存活測試..................................................................... 137 附錄二十三 DVD-R 藍光光碟簡介.................................................................. 139 附錄二十四 FMD 螢光多層光碟簡介.............................................................. 141zh_TW
dc.language.isoen_USzh_TW
dc.publisher化學工程學系zh_TW
dc.subject雙胺酯zh_TW
dc.subjectIsocarbostyrilen_US
dc.subject單胺酯zh_TW
dc.subject二苯乙醛zh_TW
dc.subject苯乙烯胺酯zh_TW
dc.subject烯醇式zh_TW
dc.subjectEnol Ether Formen_US
dc.titleResearch on General Synthesis of Polymer Intermediates Possessing 3-, 4-Isocarbostyril Groupsen_US
dc.title含3-,4-Isocarbostyril團基之高分子中間體的一般合成方法及研究zh_TW
dc.typeThesis and Dissertationzh_TW
item.openairetypeThesis and Dissertation-
item.fulltextno fulltext-
item.cerifentitytypePublications-
item.grantfulltextnone-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.languageiso639-1en_US-
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