臺灣博碩士論文加值系統

摘 要
1-氯-2-(1-氯-3-三甲基矽基-2-丙炔基)-3-甲基矽基環丙烷 （18） 在室溫下與矽藻土和水均勻攪拌三天，可生成氫氧取代產物 19、20。若將化合物 18 與 1 當量硝酸銀水溶液反應後，則可得到取代以及脫除反應的產物 23、24。將化合物 19 與 1 當量氟離子反應生成化合物 23，純化後再與 1.2 當量氟離子在加熱條件下反應可得到 3-(1-氫氧基-2-丙炔基)-環丙烯，並以 DPIBF（diphenyliso- benzofuran） trapped 證明之。將化合物 23 在 0℃ 之下與 Pd(PPh3)4、CuI 進行 coupling 反應，可得到參鍵相連的產物 30，並且在室溫下與 2 當量氟離子反應可得到脫除單邊與雙邊的環丙烯，並以 DPIBF（diphenylisobenzofuran） trapped 證明之。
另外，化合物 23 的非鏡像異構物 24 在 0℃ 之下與 Pd(PPh3)2Cl2、CuI 進行 coupling 反應後，也可以生成參鍵相連的產物 31。

Abstract

1-Chloro-2-(1-chloro-3-trimethylsilyl-2-propynyl)-3-trimethylsilylcycloproane （18） was stirred with silica gel and water at room temperature for three days to give hydroxyl-substituted adducts 19、20. Compound 18 was treated with 1 equivalent silver nitrate in wet THF solution to give substituted and eliminated adducts 23、24. After compound 19 was treated with 1 equivalent of tetrabutylammonium fluoride to give adduct 23. Compound 23 was treated with 1.2 equivalents of tetrabutylammonium fluoride at THF refluxing temperature to give 3-(1-hydroxyl-2-propynyl)cyclopropene, which was trapped by DPIBF. Compound 23 underwent coupling reaction with Pd(PPh3)4、CuI at 0 ℃ to give diyne 30. Diyne 30 reacted with 2 equivalents of tetrabutylammonium fluoride at room temperature to give single and double eliminated products, 30a and 30b, which were trapped by DPIBF.

Furthermore, compound 24, a diastereomer of compound 23, also underwent coupling reaction with Pd(PPh3)2Cl2、CuI at 0 ℃ to give diyne 31.

目 錄
中文摘要..................................................i
英文摘要.................................................ii
一、 緒論.................................................1
1-1 前言..............................................1
1-2 Cyclopropenes 的性質...............................4
1-3 Methylenecyclopropene 的性質......................5
1-4 Benzocyclopropene 的性質...........................5
1-5 末端炔類的反應....................................6
1-6 研究目標..........................................8
二、結果與討論...........................................11
結論.................................................22
三、實驗部分.............................................23
3-1分析儀器及藥品...................................23
3-2實驗步驟與光譜數據...............................25
四、參考資料.............................................36
五、光譜資料.............................................38
六、附錄：X-ray 單晶繞射資料.............................65

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