釕金屬錯合物與含酚之丙炔亞胺反應之研究

利用水楊醛 (2-hydroxybenzaldehyde) 及丙炔胺進行脫水反應，我們製備出了一個含有酚環在其上的丙炔亞胺化合物1a，且隨著醛類起始物選擇的不同，相似於1a的另外三種丙炔亞胺化合物1b – 1d亦被合成出來。當我們將1a – 1c與[Ru]-Cl反應一夜後，會得到一組由陽離子釕金屬亞乙烯基錯合物([Ru]=C=CHR) 2a – 2c及碳烯 (carbene) 錯合物3a – 3c組成之混合物為反應後之產物，其中碳烯 (carbene) 錯合物3a – 3c為主要產物，而亞乙烯基錯合物 ([Ru]=C=CHR) 2a – 2c為次要產物。隨著反應時間的加長，我們可以得到3a – 3c為最終的產物。有趣的是，當相同的反應條件用以操作在1d與[Ru]-Cl的反應時，一夜的反應時間後，我們得到亞乙烯基錯合物2d為單一產物。然而，當反應時間拉長至7天，其他無法辨識的副產物除外，我們仍然可以觀察到相似的3d產物生成。亞乙烯基錯合物2及碳烯錯合物3的鑑定是藉由31P NMR、1H NMR以及2D NMR光譜的數據資料。亞乙烯基錯合物2上的配基是從1的分子轉換而來；碳烯錯合物3上的配基則是在2的alpha碳及beta碳之間加上一鄰-甲酚結構的分子碎片進而得到一個含”色烯(2H-chromene)”分子單元的配基，分別在”色烯(2H-chromene)”分子單元的3號跟6號位置有若干個不同的取代基。在3b的質譜中，m/z 1014.24的訊號亦與我們推測的結構相符。在我們的研究中，加成上去的鄰-甲酚分子是來自有機亞胺化合物而非醛類化合物。當兩個不同丙炔亞胺化合物同時加到反應系統中與[Ru]-Cl進行反應時，我們可以得到一個新的碳烯錯合物。從質譜上的數據來觀察，此碳烯錯合物是由不同的丙炔亞胺錯合物中個擷取部分分子結構而形成交錯碳烯錯合物。因此，我們相信，在亞乙烯基錯合物2上進一步進行加成上鄰-甲酚分子，進而得到碳烯錯合物3的反應過程中，亞胺的官能基想必扮演著相當重要的角色。此外，針對1b的亞胺官能基進行還原反應後，我們合成出相對的丙炔胺化合物5b以進行上述反應之研究。5b的丙炔及酚的官能基都是被保留的。隨著亞胺官能基的轉變，我們觀察到不同的反應性。

關鍵字

亞胺；亞乙烯基錯合物；釕；含氧碳烯基；環化

並列摘要

Compound 2-((prop-2-ynylimino)methyl)phenol (1a), a propargyl aldimine, is prepared from the condensation of 2-hydroxy benzaldehyde and propargyl amine. Three analogous compounds 1b, 1c and 1d are prepared similarly, using different aldehydes as starting materials. The reactions of compounds 1a – 1c with [Ru]-Cl ([Ru] = RuCp(PPh3)2) in the presence of NH4PF6 in CH2Cl2 at room temperature for one day afford the corresponding carbene complexes 3a – 3c as the major products and the vinylidene complexes 2a - 2c as the minor products, respectively. For a longer reaction time, the same reaction afforded, in high yield, the carbene complexes 3a – 3c without 2a – 2c. Interestingly, the overnight reaction of compound 1d under the same reaction condition affords complex 2d as the only product. Lengthening the time for 7 days results in similar carbene complex 3d with some by-products. Structures of complexes 2a – 2d and 3a – 3d are proposed on the basis of spectroscopic data. The vinylidene ligand of complex 2 is from complete conversion of 1. The ligand in complex 3 resulted from addition of a o-cresol moiety to C alpha and C beta of the vinylidene ligand of 2 to yield a substituted 2H-chromene unit, with various substituents on the 3,6-positions. In the mass spectrum of 3b, the parent peak at m/z 1014.24 confirms the proposed structure. Through our study, the added o-cresol portion comes from the organic imine compounds 1, instead of aldehyde. When two imines with different substituents were used in the reaction, new cross carbene complex formed from coupling of two imine molecules as evidenced by the mass spectrum. Therefore, the imine group plays a decisive role when the addition of an o-cresol moiety to the vinylidene ligand occurs. Furthermore, the amine analogue 5b, which retains the propargyl group and phenol moiety, is treated with [Ru]-Cl under the same reaction condition. Completely different reactivities are observed when the imine functionality of the Schiff base used in our study is transformed to the corresponding amine group.

並列關鍵字

Imine ； vinylidene ； ruthenium ； oxocarbene ； cyclization

參考文獻

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釕金屬錯合物與含酚之丙炔亞胺反應之研究

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