臺灣博碩士論文加值系統

摘 要
本論文主要探討以二碘化釤/六甲基磷醯胺試劑促進2-口塞吩甲酸乙酯與酮類進行二次還原性親電性加成反應及其偶合產物之衍生物應用於液晶及光變色等材料性質研究。
於二次還原性親電性加成反應方面：2-口塞吩甲酸乙酯及一系列酮類利用二碘化釤/六甲基磷醯胺試劑為反應系統條件下，可順利進行二次還原性親電性加成反應，獲得高度立體選擇性之偶合化合物。其產物再依序進行脫水反應、聯繼性氧化反應-電子環化反應-氧化反應，便可合成多種不同取代基的三聯苯并口塞吩化合物、多苯并口塞吩化合物及含口塞吩之多環化合物。
於衍生應用方面：若將其偶合化合物利用脫水反應、一次氧化反應合成含口塞吩之共軛三烯類化合物M，探究經由光化學反應產生異構化現象，所造成化合物本身感官顏色變化機制，與其化合物自身物理光學性質之研究。
另一方面，二次還原性親電性加成反應之偶合產物，經由脫水反應、氧化反應所獲得含口塞吩之雙烯類化合物37、三烯類化合物38
及三聯苯并口塞吩化合物39，於適當取代基的搭配下，發現具有液晶現象。藉此激發起探討其化合物於不同長碳鏈或中心結構改變對於液晶性質變化之研究。

Abstract
In this thesie, I describe the reductive double electrophilic coupling reactions of ethyl thiophene-2-carboxylate and ketones promoted by SmI2/HMPA and application of these compounds in the areas of liquid crystals and photochromism are under study.
Ethyl thiophene-2-carboxylate underwent the reductive double electrophilic coupling reactions with aryl ketones by promotion of SmI2/HMPA to give disubstituted 4,5-dihydrothiophene-2-carboxylates in high regio- and stereoselective manner. The products obtained from the reductive double electrophilic reactions of ethyl thiophene-2-carboxylate were converted to thiophene-fused p-terphenyls, polybenz[b]thiophenes and thiophene-fused polycyclic compounds via sequential oxidation-electrocyclization-oxidation reactions.
The SmI2-promoted coupling reactions of ethyl thiophene- 2-carboxylate with aryl ketones, followed by acid-catalyzed dehydration and oxidative aromatization gave dialkenylthiophenes M which under went electrocyclizations upon irradiation to give the corresponding closed-ring species N constitutes a novel photochromic system.
By a simplar procedure, dienes 37, trienes 38 and benzothiophenes 39 bearing long-chain substitutents were prepared. Among them, dienes 37 and trienes 38 possess the liquid crystalline properties of smectic-A type. Thieno-p-terphyls 39 exist as solids with rather high melting points, even though they are equipped with soft long chains of decoxy, dedecoxy, tetradecoxy and hexadecoxy groups. By comparison with the thienyl rings in 37 and 38, the rigid core of benzothiophene is longer to disfavor the liquid-crystalline property.

目錄
簡語對照表………………………………………………………………….i
表目錄……………………………………………………………………….ii
圖目錄……...……………………………………………………………….ix
中文摘要……………………………………………………………………vi
英文摘要…………………………………………………………………..viii
緒論………………………………………………………………………….1
結果與討論…………………………………………………………….....8
第一章 2-口塞吩甲酸乙酯與酮類三成份聯繼性偶合反應之研究及其衍生應用………………...………………………………………………8
1-1前言…………………………...………………………………………8
1-2 一鍋式聯繼性二次還原親電性反應(One Pot Sequential Double
Reductive Electrophilic Reactions)………………………..……….11
1-2.1 一分子2-口塞吩甲酸乙酯與二分子對位取代之苯乙酮一鍋式
聯繼性交錯偶合反應…………….…………..………….11
1-2.2 一分子2-口塞吩甲酸乙酯與二分子環酮一鍋式聯繼性交錯偶合
反應…………………………………………………..……….14
1-2.3 一分子2-口塞吩甲酸乙酯與多取代苯甲基苯酮一鍋式聯繼性交
錯偶合反應………………………………..………………….16
1-3 聯繼性二次還原親電性偶合反應之反應機構探討………………20
1-4 衍生應用---多取代基苯并口塞吩化合物之合成……………………23
1-4.1 傳統苯并口塞吩中心骨架之設計策略……….……...……...….23
1-4.2 新式多取代基苯并口塞吩化合物之合成策略---聯繼式氧化-電
子重排環化-再氧化反應(Sequential oxidation electrocyclization
-oxidation reaction)…………………………………………….25
1-4.3 三聯苯并口塞吩、多聯苯并吩化合物之合成………….…..26
1-5 多取代基苯并口塞吩化合物吸收光譜與螢光之研究…………..…..35
1-5.1三聯苯并口塞吩化合物12吸收光譜與螢光之比較…………...35
1-5.2多聯苯并口塞吩化合物14及多苯并口塞吩化合物吸收光譜、螢光
之比較……………………………………………..………36
1-6 結論…………………………………………………………..….41
第二章 含口塞吩共軛三烯類化合物之合成及其光變色性質研究……….42
2-1 基本介紹…………………………………………………………..42
2-1.1 光變色物質之定義及其價值…………………..……….…42
2-1.2 光變色物質之分類………………………………….….…43
2-2 新型光變色分子---含口塞吩共軛三烯類化合物之設計原理……....47
2-3 含口塞吩共軛三烯類化合物之合成及其性質討論……..……….….49
2-3.1 4,5-雙芳香基口塞吩化合物16a及16b於光反應下吸收光譜之
變化研究……………….………....…………………………...49
2-3.2 含口塞吩共軛三烯類化合物之合成……………….…….…50
2-4 捕捉中間體(trapping intermediate)---Diels-Alder反應…………...62
2-5 未來展望…………………………………………………………....66
第三章 含口塞吩化合物液晶之設計合成及其性質研究………………….67
3-1 液晶概論………………………………………………...…….67
3-1.1 前言…………………………………………………….…..67
3-1.2 液晶之分類及其排列形態……………………..……...…68
3-1.3 液晶的觀察及識別………………………………………...69
3-1.4 另類特殊功能液晶材料…………………………………...71
3-2液晶之設計原理……………………………………………….…75
3-3苯并口塞吩化合物液晶之合成及其性質研究………………….…79
3-3.1 三聯苯并口塞吩化合物之設計合成與其液晶相性質研究…..79
3-3.2 多聯苯并口塞吩化合物之設計合成與其液晶相性質研究......89
3-3.3 未來展望……………………………………………..…….91
3-4 結論…………………………………………………………………93
結語………………………………………………………………….…..95
實驗部分…………………………………………………………………...97
參考文獻………………………………………………………….....174
附錄…………………………………………………………………..181

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