臺灣博碩士論文加值系統

本論文成它X成出有機鎢金屬路易士酸催化劑[N(CH2-2-py)3W(CO)(NO)2](BF4)2，而此路易士酸是以W(CO)6在CH3CN溶劑中進行迴流加熱二十四個小時後，將部分的溶劑抽乾後，再加入N(CH2-2-py)3與兩當量NOBF4在0oC下反應90分鐘，便可得到綠色的路易士酸[N(CH2-2-py)3W(CO)(NO)2](BF4)2。此催化劑為零價的有機鎢金屬錯合物，當一氧化碳配位基離去後，所展現的路易士酸度介於AlCl3和BF3之間 (Δδ = 1.18 ppm ) ，並且對於水的穩定性極高，在溶液中能維持48小時以上而不會分解 (decomposed) ，對於水的溶解度可達37 g/L。而[N(CH2-2-py)3W(CO)(NO)2](BF4)2催化劑在固態和液態的結構是不同的;在固態下，從催化劑的晶體結構可以得知，N(CH2-2-py)3是以四配位的形式配位在中心金屬上;而其液態結構推測NMR光譜顯示N(CH2-2-py)3與中心金屬具有多種的η3與η4的配位形式，主要是因為催化劑上的一氧化碳配位基離去後，可藉由快速η3和η4互相快速轉換來穩定催化劑16電子的結構 ( η4-N(py)3W、η3-N(py)2W、η3-(py)3W ) 。
本論文主要重點是將此有機鎢金屬路易士酸應用於Biginelli縮合催化反應中，並以綠色化學為宗旨選擇以催化劑、傳統對流加熱法、微波、改變反應溶劑系統等因素探討對Biginelli縮合反應的影響。在傳統對流加熱，以乙醇 (CH3CH2OH) 、二甲基甲醯胺 (DMF) 、乙酸乙酯 (EA) 或[Bmim]BF6 (1-butyl-3-methylimdazolium hexafluoro-phosphate) 室溫離子液體為反應溶劑，在80oC下只需利用少量 (0.6 mol%) 的[N(CH2-2-py)3W(CO)(NO)2](BF4)2催化劑，針對三種不同的起始物 (乙酸乙酯、醛類、尿素) ，進行Biginelli縮合反應得到非常高的二氫嘧啶產率；除此之外，當乙酸乙酯接有強拉電子基時，具有較佳之反應性，其反應活性如下所示 : 4-氯乙醯乙酸乙酯 > 乙醯乙酸乙酯。另外，在二甲基甲醯胺(DMF)或 [Bmim]BF6 (1-butyl-3-methylimdazolium hexafluoro-phosphate) 室溫離子液體中改以微波照射，可大幅減低反應時間，提升催化效率。

We have successfully synthesized the organotungsten Lewis acid, [N(CH2-2-py)3W(CO)(NO)2](BF4)2 (3) in quantitative yield by treating W(CH3CN)3(CO)3 with N(CH2-2-py)3 (tpa) in the presence of 2 equiv. of NOBF4 in CH3CN at 0 oC for 90 minutes. The complex 3 is very moisture- and air-stable. Its crystalline solid form can be stored in air for months and its solution can also stay unchanged for at least 48 hours without detectable decomposition. In addition, complex 3 has a relatively high water-solubility of 37 g/L and possesses strong Lewis acidity upon loss of the CO ligand. The Lewis acidity of [N(CH2-2-py)3W(CO)(NO)2]2+ measured by 1H NMR method falls between those found for AlCl3 and BF3. But the complex [N(CH2-2-py)3W(CO)(NO)2]2+ exhibits very different structures in solid state and in solution. The crystal structure of 3 shows the tpa ligand in its h4-coordination mode bound to the W center. While in solution state, tpa has various coordination possibilities (h3- or h4-interconversion) as suggested by its 1H NMR spectral data. Because the lability of CO ligand, the resulting 16-e species (the real active catalyst) could be further stabilized by the formation of the 4th W－N bonding via a fast h3-to-h4 interconversion.
The three-component Biginelli condensation reaction is one of the most widely applied method for the synthesis of 3,4-dihydropyridine-2(1H)-one (DHPMs). This one pot reaction involves the condensation of ethyl acetoacete, aldehyde and urea in the presence of a variety of acidic condensing agents. In this dissertation a series of Biginelli condensation reactions were catalyzed by a novel organotungten Lewis acid [N(CH2-2-py)3W(CO)(NO)2](BF4)2 (3). With the employment of as little as 0.6 mol% of catalyst 3, the condensation reactions were efficiently proceeded in molecular solvent systems such as DMF or in a thermally stable room temperature ionic liquid, BmimPF6 (1-butyl-3-methylimidazolium hexafluorophosphate). We have also investigated the congregating effect of this Lewis acid under microwave irradiation conditions. In all cases, a dramatic reaction rate-enhancement from hours to minutes was observed under microwave irradiation conditions as compared to those found by using thermal heating method. In addition, it has been demonstrated that catalyst 3 can be selective and as effective towards organic base functionality.

總目錄
頁次
圖目錄-----------------------------------------------------------------------------III
表目錄-----------------------------------------------------------------------------V
附圖目錄------------------------------------------------------------------------VII
附表目錄------------------------------------------------------------------------IX
中文摘要-------------------------------------------------------------------------X
英文摘要------------------------------------------------------------------------XII
一、緒論---------------------------------------------------------------------------1
1.1. Biginelli縮合反應及其應用--------------------------------2
1.2. 綠色化學-----------------------------------------------------------------11
1.3. 綠色化學與微波反應-------------------------------------------16
1.4. 研究動機----------------------------------------------------------20
二、實驗部分-------------------------------------------------------------------24
2.1. 一般敘述----------------------------------------------------------24
2.2. 儀器設備----------------------------------------------------------28
2.3. 實驗合成部分----------------------------------------------------30
2.4. 在微波照射下進行Biginelli縮合反應-------------------49
三、結果與討論------------------------------------------------------------------50
3.1 前驅物[N(CH2-2-py)3W(CO)3] (2) 的晶體結構------------------51
3.2 催化劑[N(CH2-2-py)3W(CO)(NO)2] (BF4)2 (3) 的合成與
晶體結構-----------------------------------------------------------------55
3.3 Biginelli縮合反應--------------------------------------------------63
3.4 有機鎢金屬路易士酸催化催化劑3 催化Biginelli縮合
反應之反應機制--------------------------------------------------------90
四、結論---------------------------------------------------------------------------------93
五、參考文獻---------------------------------------------------------------------------95
附圖------------------------------------------------------------------------------------101
附表------------------------------------------------------------------------------------134

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