脱羧二苯并吡喃酮生成反应及醇与三级胺交换反应的分析-analysis of decarboxylation reaction of benzopyranone and exchange reaction between alcohol and tertiary amine.docxVIP

湘潭大学 湘潭大学 2012 届硕士学位论文 II II Abstract With the rapid development of society, how to protect environment and realizing sustainable development has become an unavoidable problem. All these show severe challenges to chemical researchers. Therefore, the concept “green chemistry” was put forward in the early 1990 s, that is how to reduce or even eliminate pollution. According to the environment friendly development need, combined with the research of our group, this paper did some exploration about construction of C-C and C-N bond. Herein, we reported the research of one-pot synthesis of dibenzopyranones via decarboxylation and amination of alcohols with tertiary amines. Some detailed research was described as follows: We reported a Pd/Cu-based catalyst systems for dibenzopyranones synthesis reactions. Dibenzopyranone motifs are present in many natural products and biolo- gically active molecules. Traditional lactone synthesis mainly relies on Suzuki- Miyaura reaction from the corresponding boronic acids and aromatic halides. However, these methods generally require several steps and include the purification of the intermediates. Also, boronic acids are relatively expensive and hard to store. Thus, we had developed a one-pot synthesis of dibenzopyranones via a decarboxylative cross-coupling and lactonization sequence based on the common and cheap raw material aromatic carboxylic acids. We did the pilot studies of the mechanism of the reaction, and we believed that the reaction may undergo decarboxylative cross- coupling between carboxyl and halogenated aromatics then followed by lactonization of ester and nitro group. Besides, we reported a ruthenium-catalyzed unsymmetric tertiary amines formation from direct amination of alcohols with tertiary amines. We began our investigation by using p-methylbenzyl alcohol and tributylamine as a model. We found that ruthenium catalyst system catalyzed efficiently, yielding unsymmetric tertiary amines in yields up to 87%. The reactio