壹、beta-硝基苯乙烯的應用—4-芳基四氫異喹啉、3-芳基吲哚、2-芐基苯並呋喃及2-芳基色滿衍生物的合成 貳、茚並異喹啉的合成

Abstract

本論文分為兩個章節，每章節各自獨立，包含前言、研究目標、實驗結果 與討論，以及結論。 第壹章節探討beta-硝基苯乙烯衍生物在化學合成上的發展性與應用性，可以分為四個部分，分別為4-芳基四氫異喹啉、3-芳基吲哚、2-芐基苯並呋喃及2-芳基色滿四種化合物的合成。第一部分，beta-硝基苯乙烯與芳環用三氯化鋁催化傅-克烷化反應合成硝基烷，其還原後的胺類以傅-克反應或皮克特-施彭格勒反應得到4-芳基四氫異喹啉衍生物；若將胺類以銅試劑催化烏爾曼反應則是新穎的3-芳基吲哚合成法，為第二部分。第三部分，將beta-硝基苯乙烯衍生物還原為硝基烷，經過內夫反應合環得到2-苄基苯並呋喃；第四部份則將硝基烯衍生物作為中間產物，在鹼催化下一鍋化合成2-芳基色滿。 第貳章節為茚並異喹啉的合成，分成三個部分，第一部分以2-碘苯甲醯胺與茚滿二酮為起始物，在乙腈中銅催環化反應得到茚並異喹啉衍生物。第二部分為第一部分的反應條件的改良，除了將溶劑改為水，也縮短了反應時間跟減少銅試劑的使用量。第三部分為茚並異喹啉的合成展望，嘗試由2-鹵苯甲酸與茚滿二酮作為起始物，在反應過程中加入胺類以一鍋化合成茚並異喹啉衍生物，可減少合成步驟並提升原子效益。

The content of the thesis is divided into two chapters, each chapter individually including preface, research goal, results and discussions, and conclusion. Chapter I discuss about the applicability of beta-nitrostyrene derivatives for the synthesis of four types of structurally different compounds such as 4-aryltetrahydroisoquinoline, 3-arylindole, 2-benzylbenzofuran and 2-arylchroman derivatives. This chapter is divided into four parts. In the first part, the amines derived from nitroalkanes, which was synthesized via AlCl3-catalyzed Friedel-Crafts alkylation and reductive amination of beta-nitrostyrenes and arenes, underwent Friedel-Crafts cyclization or Pictet-Spengler reaction to produce 4-aryltetrahydroisoquinolines. In the second part, the amines were treated with copper catalyst to furnish 3-arylindoles. For third and fourth parts, nitroalkene derivatives modified from beta-nitrostyrenes were subjected to Nef reaction to yield 2-benzylbenzofurans, or treated with base to do Michael addition to obtain 2-arylchroman derivatives. Chapter II is the synthesis of indenoisoquinolines, and is divided into three parts. The first part using 2-iodobenzamides and 1,3-indandiones as starting materials, which were transformed into indenoisoquinoline derivatives by copper-catalyzed cyclization in acetonitrile . The second part deals with the water-mediated synthesis of the same compounds under reduced amount of copper catalyst. The third part is a progressive project. We replaced 2-iodobenzamides with 2-halobenzoic acids as starting materials, after coupling with 1,3-indandione the amine derivative could be inserted and cyclized to afford the desired indenoisoquinolines. This one-pot water-mediated synthesis can save synthetic steps and improve atom efficiency.