- 學位論文
烯雙炔類及其相關化合物與疊氮化鈉之環化反應探討
Studies on the Cyclization Reactions of Enediynes and Related Molecules with Sodium Azide
摘要
本論文探討三個烯雙炔及相關衍生物與疊氮化鈉的不同反應。第 一部分，我們取 (Z)-1,6-二取代基-3-己烯-1,5-雙炔與疊氮化鈉在二甲 基亞碸中，於80 oC 下，可得到1,2,3-三唑[1,5-a]吡啶；各式的對稱或 不對稱的烯雙炔類在此條件下可得到中等至不錯的產率。第二部分， 我們討論在微波加熱下，2-炔基腈苯與疊氮化鈉反應，4,5-二取代基 -2H-1,2,3-三唑類化合物或是四唑[5,1-a]異喹啉類化合物可以選擇性地被合成；2-苯乙炔基腈苯與5 當量疊氮化鈉，在二甲基亞碸中，直接加熱下，可得到產率98%的4-(2-腈基苯基)-5-苯基-2H-1,2,3-三唑；而若添加了8 當量溴化鋅，則得到是產率43%的5-苯基四唑[5,1-a] 異喹啉及50%的回收起始物；我們發現微波加熱能夠加速此反應的反 應速率。 有趣的是，在微波加熱下，2-(5-氫氧基戊-1-炔基)腈苯類化合物 與疊氮化鈉反應得到的是4-胺基-2,3-二氫萘并[2,3-b]呋喃類化合物。 我們以甲醇鈉替換疊氮化鈉，並改為油浴加熱，使反應溫合進行並提 高產物了產率。所有的細節本論文裡有更詳盡介紹。
並列摘要
In this dissertation, three different reactions of enediynes and related molecules with sodium azide are presented. In the first part, the reactions of (Z)-1,6-disubsituted-3-hexen-1,5-diynes with sodium azide in DMSO at 80 oC to give 1,2,3-triazolo[1,5-a]pyridine are described. Various symmetrical or unsymmetrical enediynes were carried out in this study and led to the products formation in modest to good yields. In the second part, the selective syntheses of 4,5-disubstituted-2H-1,2,3-triazoles and tetrazolo[5,1-a]isoquinolines by the reactions of 2-alkynylbezonitriles with sodium azide under microwave irradiation are described. Heating 2-(2-phenylethynyl)benzonitrile with five equivalents of sodium azide in DMSO gave 4-(2-cyanophenyl)-5-phenyl-2H-1,2,3-triazole in 98% yield. However, in the presence of eight equivalents of ZnBr2, the reaction gave 5-phenyltetrazolo[5,1-a]isoquinoline in 43% yield and the recovered starting material in 50% yield. We found the reaction rates could be accelerated under microwave irradiation. Interestingly, when 2-(5-hydroxypent-1-ynyl)benzonitriles were treat with sodium azide under microwave irradiation, the reaction gave 4-amino-2,3-dihydronaphtho[2,3-b]furans. In oil bath, when sodium azide was replaced by sodium methoxide, the reaction proceeded much smooth and gave the products in better yields. All the details are discussed in the dissertation.