吡啶-喹啉酮配位基之鈀金屬錯合物的合成與催化探討

Synthesis and Catalytic Application of Palladium Complexes with a Pyridinyl- Quinolinone Ligand

10.6342/NTU201601874

鐘宏明

鉗合配位基 ； 喹啉酮 ； 鈀金屬錯合物 ； Wacker oxidation ； 亞硝基胺化合物 ； pincer ligand ； quinolinone ； palladium complex ； Wacker oxidation ； N-nitrosoamine

國立臺灣大學化學系學位論文

2016年

碩士

劉緒宗

繁體中文

本論文主要是含吡啶-喹啉酮配位基之鈀錯合物的合成與性質探討。2-氯-8-羥基喹啉與 2-(溴甲基)吡啶進行親核取代反應生成 2-氯-8-(2-吡啶甲氧基)喹啉 (5)，再以醋酸水解合成 8-(2-吡啶甲氧基)喹啉酮 (6)，作為所探討的配位基。將6與 (CH3CN)2PdCl2 反應，可得到中性的鈀金屬錯合物 [Pd(6)Cl]2 (7)，並由氫譜、碳譜、質譜以及X光單晶繞射分析儀鑑定其結構。 該錯合物具有催化C=C雙鍵的氧化裂解性質，一般苯乙烯的加水反應大多生成苯乙酮，而鈀錯合物7可以在溫和的條件下成功催化雙鍵進行加水反應而生成的末端醛化物，並且進一步氧化裂解生成苯甲醛產物。此研究亦針對鈀錯合物7對於不同類型的不飽和鍵的反應物，作催化探討。 論文另一部分，則探討亞硝基胺化合物( 10a-b, 14 )的反應性。利用低價數的銠金屬催化下，化合物 10a-b 會進行不對稱的偶合反應生成化合物 (11)；而鉬金屬將化合物 14 進行環化反應，成功得到化合物 (15) 。

The main work of this thesis involves the synthesis and application of palladium complexes with a pyridinyl-quinolinone ligand. Nucleophilic substitution of 2-(bromo-methyl)pyridine with 2-chloroquinolin-8-ol under basic conditions provided 2-chloro-8-(pyridin-2-ylmethoxy)quinoline, which was further hydrolyzed in acetic acid to yield the desired ligand, 8-(pyridin-2-ylmethoxy)quinolin-2(1H)-one (6). Complexation of 6 with (CH3CN)2PdCl2 gave the corresponding complex 7. The structure of 7 was characterized by 1H /13C NMR and mass spectroscopic methods, and further confirmed by X-ray crystallography. Complex 7 can act as a catalyst for oxidative cleavage of C=C bonds. Acetophenones is usually obtained from the metal catalyzed hydration of styrenes via the Wacker process. In our research, the hydration of styrenes catalyzed by 7 provided the terminal aldehyde as the initial product, which was further oxidized to yield benzaldehyde. Systematic studies of this catalysis were discussed. The other work involves the investigation of the reactivity of nitrosoamine keto-compounds (10a-b, 14). Reaction of 10a-b under a rhodium-catalyzed condition rendered 11 as the major product, resulting from a coupling of vinyl phenyl ketone. On the other hand, treatment of 14 with formic acid in the presence of Mo(CO)6 as a promoter underwent the cyclization to afford pyrrolidine 15.

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