中文摘要 本論文主要是研究4-乙氧基-1-乙氧羰基薁之3-位置醯化反應,合成4-乙氧基-1-乙氧羰基-3-烷醯基薁(甲醯基、乙醯基、三氟乙醯基),再利用4-乙氧基-1-乙氧羰基-3-烷醯基薁在乙醇為溶劑室溫下與聯胺,苯聯胺,乙二胺或鄰苯二胺的反應,可合成五、七、六三環雜環化合物:1-乙氧羰基-5,6-二氫-5H-薁併[1,8a,8-c,d]-1,2-二氮-陸圜 (30)、1-乙氧羰基-3-甲基-5,6-二氫-5H-薁併[1,8a,8-c,d]-1,2-二氮-陸圜 (35)、1-乙氧羰基-3-三氟甲基-5,6-二氫-5H-薁併[1,8a,8-c,d]-1,2-二氮-陸圜 (36)、1-乙氧羰基-3-三氟甲基-4-N-苯基-5,6-二氫-5H-薁併[1,8a,8-c,d]-1,2-二氮-陸圜 (38),及五、七、八三環雜環化合物:2-乙氧羰基-7H-8,9-二氫-薁併[1,8a,8-c,d]- 1,4-二氮-捌圜 (39),2-乙氧羰基-7H-8,9-二氫-苯併-薁併[1,8a,8-c,d]-1,4-二氮-捌圜 (40)。 其反應路徑為胺基先與薁核3-位醯基形成希夫鹼(Schiff base)另一端胺基再與薁核4-位置的乙氧基進行取代,中間體具有穩定的富烯(fulvene)結構。 此外,4-乙氧基-1-乙氧羰基-3-氰基薁在相同的情況下,也可與聯胺作用,合成五、六、七三環雜環化合物,1-乙氧羰基-3-胺基-5,6-二氫-5H-薁併[1,8a,8-c,d]-1,2-二氮-陸圜 (37)。
Abstract This thesis studies the formation of 4- ethoxy- 1- ethoxycarbonyl azulene, the synthesis of 4- ethoxy- 1- ethoxycarbonyl- 3- Razulene (formyl, acetyl, trifluoroacetyl), then 4- ethoxy-1- ethoxycarbonyl - 3-Razulene reacts with hydrazine, phenylhydrazine, ethylenediamine, o-phenlenediamine, afford five, seven, six member heterocyclic compound : 1-ethoxycarbonyl-5, 6-dihydro-5H-azuleno[1,8a,8-c,d]-1, 2-diazoine (30) , 1- ethoxycarbonyl- 3-methyl- 5,6- dihydroazuleno[1,8a,8-c,d] -1, 2- diazoine (35), 1-ethoxycarbonyl- 3- trifluoromethyl- 5,6-dihydroazuleno -[1,8a,8-c,d] -1, 2- diazoine (36), 1- ethoxycarbonyl- 3- trifluoromethyl- 4- N-phenyl- 5, 6- dihydroazuleno[1,8a,8-c,d]- 1, 2- diazoine (38). And five, seven, eight member heterocyclic compounds: 2-ethoxycarbonyl -7H-8,9 - dihydroazuleno[1,8a,8-c,d]-1,4- diazocine (39), 2-ethoxycarbonyl -7H-8,9 -dihydro-benzo[b]azuleno[1,8a,8-c,d]-1, 4- diazocine (40). The path of reaction shows that the amino group reacts with 3-acetyl group to afford Schieff base, then the other amine group reacts with 4-ethoxyl, and the intermediate has stable fulvene structure. The 3- cyano- 4- ethoxyl- 1-etohylcarbonylazulene 7 also can react with hydrazine in room temperture, afford five, seven, six heterocyclic compound : 1- ethoxycarbonyl- 3- amino- 5H- 5, 6- dihydroazuleno [1,8a,8-c,d]- 1, 2- diazoine (37).