臺灣博碩士論文加值系統

本篇論文主要是研究3-苯乙烯基呋喃在鹼性條件下進行光重排反應合成2-甲基萘化合物。利用Wittig和Wittig-Horner方法合成一系列3-苯乙烯基呋喃衍生物，在含0.09M KOH的甲醇/水(19/1)溶液及含0.023M DBU、0.018M乙醇的苯溶液兩種條件下進行照光反應都能得到2-甲基萘化合物，產率約(20~61%)。
此新的光化學反應的反應機構：一開始經由順反異構化反應轉成順式起始物(1)，接著進行六電子環化反應形成中間物，在鹼催化反應下進行除去反應形成萘結構的中間體，再經由質子化反應、烯醇與醛的轉換而得到萘基乙醛中間體，最後再進行Norrish Type 1的光反應而得到產物2-甲基萘化合物。
利用還原劑NaBH4的甲醇/KOH水溶液下進行照光反應，證明反應中間體2-(萘-2-基)乙醛的存在。也利用加熱反應確認反應只會經由照光形成，並用文獻說明各種反應結果，包括取代基效應、溴取代的脫溴反應…等。

This thesis studies on photorearrangement of 3-styrylfurans to synthesize 2-methylnaphthalenes in basic media. A series of reactants, 3-styrylfurans, was synthesized by Wittig or Wittig-Horner reactions. Irradiation of these reactants in methanol/water (19/1) with 0.09 M KOH or in benzene with 0.018 M ethanol and 0.023 M DBU gives 2-methylnaphthalenes with 20~61% yields.
A plausible reaction mechanism of this novel photochemical reaction describes as follow: trans-3-styrylfuran undergoes cis/trans isomerization reaction to give cis-3-styrylfuran. Then 6e photocyclization of cis-3-styrylfuran leads a dihydrophenanthrene-type intermediate. This intermediate subsequently progress a base-induced elimination reaction to produce an intermediate with a naphthalene structure. After protonation and tautomerization, naphthlen-2-yl-acetaldehyde is formed as another intermediate. Finally, a Norrish Type 1 reaction happens to give 2-methylnaphthalenes
We have proved the presence of naphthlen-2-yl-acetaldehyde by irradiation of 3-styrylfuran with NaBH4 in methanol/KOH solution. We also confirmed this transformation is a photochemical reaction by thermal reaction of 3-styrylfuran at 70℃ in the same solvent condition. Some special reaction results, for example substitution effect and debromination of 3-(4’-bromostyryl)fruan..etc, have also been discussed in accordance of a few of literatures.

第一章
緒論
一、有機光化學反應................................... 01
二、二苯乙烯衍生物( stilbene derivatives )之光化學反應......04
1.順-反異構化( cis-trans isomerization ) ............... 05
2.光環化反應( Photocyclization ) ..................... 06
3.光加成反應( Photoaddition ) ....................... 07
4.光重排反應( Photorearrangrment ) .................. 08
三、 鹼催化之光化學反應...............................10
四、 苯乙烯基呋喃( styrylfuran )之化學反應................12
五、 本研究工作之動機.................................14
六、 本研究工作之目的.................................15
第二章 結果與討論
一、 起始物之合成.....................................16
1. Wittig-Horner合成法...............................16
2. Wittig合成法..................................... 17
3. 兩種合成法的比較................................ 18
二、 照光反應結果
1. 照光反應的條件測試 ............................ 20
2. 起始物3-苯乙烯基呋喃1a -1m在0.09M KOH(aq)與甲醇/
水(19/1)溶劑中進行照光反應.......................23
3. 起始物對位不同取代基的3-苯乙烯基呋喃在DBU與苯/乙醇溶劑中進行照光反應........................... 29
4. 加熱對起始物的影響..............................30
5. 產物的結構鑑定..................................32
三、 反應機構之探討
1. 由起始物1g之光化學反應來探討反應機構 ..........33
結論 ................................................ 35
第三章 實驗部分
一、 儀器部分........................................ 36
二、 藥品及溶劑...................................... 37
三、 不同取代基的3-苯乙烯基呋喃之合成................ 38
四、 不同取代基的3-苯乙烯基呋喃在鹼性條件下進行照光重排
反應。...........................................43
參考文獻
附錄一：化合物一覽表..................................... 54
附錄二：起始物與產物光譜資料............................. 58

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