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研究生:葉昱圻
研究生(外文):Yeh, Yu-Chi
論文名稱:含矽基及錫基有機磷氟合成團之製備及應用
論文名稱(外文):Prepartion and Application the Synthons of Phosphono-Containing Difluoroethylene Silane and Stannanes
指導教授:蔡厚仁林孝瑞
指導教授(外文):Tsai, Hou JenLin, Xiao Rui
口試委員:蔡厚仁林孝瑞洪祐明
口試委員(外文):Tsai, Hou JenLin, Xiao RuiHon, You Ming
口試日期:2012-05-17
學位類別:碩士
校院名稱:國防大學理工學院
系所名稱:化學工程碩士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:79
中文關鍵詞:有基錫化物有基矽化物磷醯化反應二氟乙烯物Stille 偶合反應
外文關鍵詞:SilaneStannanesAcylationDifluoroethyleneStille reaction
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本研究以三氟氯乙烯 (Chlorotrifluoroethylene, F2C=CFCl) 為起始物,於 -78 oC下以正丁基鋰 (n-Butyllithium, n-BuLi) 進行去鹵素反應,形成[F2C=CF]-Li+ 中間體後與含矽試劑 (PhMe2SiCl, Me3SiCl, Et3SiCl) 進行矽化反應,製得含矽基三氟乙烯 (F2C=CFSiR3, R3 = Me2Ph, Me3, Et3) 化合物後以四氫鋁化鋰 (Lithium Aluminum Hydride, LiAlH4)作還原反應,製備出含矽基二氟乙烯類 (HFC=CFSiR3 R3 = Me2Ph, Me3) 化合物。進一步以鹼性試劑正丁基鋰進攻質子再與三價磷試劑 (Ph2PCl, (EtO)2PCl, (Et2N)2PCl, (cyc-C6H11)2PCl) 反應,利用過氧化氫 (Hydrogen Peroxide, H2O2) 進行氧化反應,將氫原子取代成含五價磷合成出含磷酸基-反式-1,2-二氟-1-矽基乙烯類化合物(R2P(O)FC=CFSiMe2Ph, R = Ph, EtO, Et2N, cyc-C6H11)。以氟化鉀 (KF) 粉末進行去矽基反應後,再以氯化三丁錫 (Bu3SnCl) 進行錫化反應,合成二苯基磷酸酯基-反式-1,2-二氟-1-三丁錫基乙烯化合物 (Ph2P(O)FC=CFSnBu3),此化合物之合成資訊還未有任何文獻報導,其可視為 Ph2P(O)FC=CF- 官能基之合成團。本研究進一步將此化合物應用於 Stille 偶合反應上,將溫度控制於 80oC,以四三苯基磷鈀 (Pd(PPh3)4) 為催化劑,碘化亞銅為共催化劑與 4-碘化硝基苯 (4-iodonitrobenzene) 進行偶合反應,成功製備出二苯基磷酸酯基-反式-1,2-二氟-1-硝基苯乙烯 (Ph2P(O)FC=CFC6H4NO2) 化合物。
Chlorotrifluoroethylene (F2C=CFCl) undergoes the dehalogen reaction with n-butyllithium (n-BuLi) at -78 oC to give the intermediate of [F2C=CF]-Li+. Silyation of [F2C=CF]-Li+ with Chlorosilane reagents (PhMe2SiCl, Me3SiCl, Et3SiCl) affords silyl-containing trifluoroethylene compound (F2C=CFSiR3, R3 = Me2Ph, Me3, Et3). Treatment of silyl-containing trifluoroethylene compound with reducing reagent lithium aluminum hydride (LiAlH4) achieves HFC=CFSiR3 (R = Me2Ph, Me3). Deprotonation of HFC=CFSiR3 with n-butyllithium, subsequent acylation with R2PCl (R = R = Ph, EtO, Et2N, cyc-C6H11) gave trans-R2PFC=CFSiR3 which oxidation with hydrogen peroxide afforded trans-R2P(O)FC=CFSiR3. Protodesilylation of trans-Ph2P(O)FC=CFSiMe2Ph with potassium fluoride (KF) and tributyltin chloride (Bu3SnCl) gave trans-Ph2P(O)FC=CFSnBu3 which can be used as a synthon in phosphorus-fluorine organic synthetic. Application of the Stille reaction for the prepared Phosphono-Containing Difluoroethylene stannanes is also carried out in this research. Reaction of trans-Ph2P(O)FC=CFSnBu3 with 4-iodonitrobenzene at 80oC under Pd((PPh3)4) catalyzst and CuI cocatalyzst gives Ph2P(O)FC=CFC6H4NO2 in good yields.
誌謝 ii
摘要 iii
ABSTRACT iv
目錄 v
表目錄 vii
圖目錄 viii
附錄圖目錄 x
1. 緒論 1
1.1 研究動機及目的 1
1.2 研究架構及方法 4
2. 文獻探討 6
2.1 合成1,2-二氟-1-乙烯化合物 6
2.2 合成含錫基及含氟之乙烯類化合物 7
2.3 烯類化合物的偶合反應 9
3. 實驗 12
3.1 實驗儀器 12
3.2 實驗藥品 12
3.3 實驗步驟 14
3.3.1 F2C=CFSiMe2Ph 合成 14
3.3.2 F2C=CFSiMe3 合成 15
3.3.3 F2C=CFSiEt3 合成 15
3.3.4 HFC=CFSiMe2Ph 合成 16
3.3.5 HFC=CFSiMe3 合成 17
3.3.6 Ph2P(O)FC=CFSiMe2Ph 合成 18
3.3.7 (EtO)2P(O)FC=CFSiMe2Ph 合成 19
3.3.8 (cyc-C6H11)2P(O)FC=CFSiMe2Ph 合成 20
3.3.9 (Et2N)2P(O)FC=CFSiMe2Ph 合成 21
3.3.10 Ph2P(O)FC=CFSnBu3 合成 22
3.3.11 Ph2P(O)FC=CFC6H4NO2 23
4. 結果與討論 24
5. 結論 40
參考文獻 41
附錄 47
自傳 65

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