伯酰胺化合物的合成及rh催化双c-h键活化分析-synthesis of primary amide compounds and analysis of rh - catalyzed activation of double c - h bonds.docx

2. 在空气氛围下，[{Cp*RhCl2}2]作为催化剂，Co(OAc)2·4H2O 作为添加剂，在 DMF 中 110 ℃条件下反应 2 小时成功实现了 2-苯基吡啶并咪唑类化合物的双 C-H 键活化，并通过与内炔烃环化得到含有吡啶并咪唑骨架的稠环化合物，产率 最高可达 97%。与 Cu(OAc)2·H2O 作为添加剂的催化体系相比，Co(OAc)2·4H2O 可以有效的促进该反应的进行，反应时间可以缩短至 2 h。3．对所合成的 11 个 5, 6-二苯基萘并[1,2:4,5]咪唑并[1,2-a]吡啶类化合物的光学性质进行了研究。研究结果表明：这些化合物在稀溶液状态和固态时均有 较好的光致发光性质。此类化合物在二氯甲烷中的发射波长集中在 400-430 nm， 表现为深蓝色发光，取代基的变化对此类化合物在二氯甲烷中的发射波长无明 显影响。II关键词：催化，伯酰胺化合物，铑，C-H 活化，2-苯基吡啶并[1,2-a]咪唑，光学性质IIIAbstractIn this dissertation, the synthesis of primary amides and rhodium catalyzed double C-H bonds activation were studied. The main contents are as follows:Amide bond formation is a fundamentally important reaction in organic synthesis. Despite their obvious importance, the existing methods concerns about their waste and expense are becoming sharper. This discrepancy has encouraged efforts towards the identification and development of more atom-efficient, catalytic methods for amide bond formation. In this dissertation, a new catalytic system that one pot conversion of aromatic aldehydes to primary amides in transition-metal-free system has been developed, and its catalytic performance has been investigated:In transition-metal-free system, the amidation of aldehydes can be carried out at 125℃ under air atmosphere. After 48 h the aromatic aldehyde could transform toprimary amides in the presence of hydroxylamine hydrochloride and Cs2CO3 in aqueous dimethyl sulfoxide (DMSO).The catalytic system can proceed the amidation of various aldehydes very well, the yield of primary amides is up to 99%.The mechanism of this catalytic system was studied. In this reaction benzaldehyde first undergo reaction with hydroxylamine to give benzaldehyde oxime that is transformed into benzamide by dehydration and hydration processes in the presence of base.In recent years, the direct formation of carbon-carbon and carbon-heteroatom bonds via C-H activation has enormous potential for advancing the field of chemical synthesis. In this field the rhodium