Cyclodienones. Part 6. Preparation of 4-azido-2,4,6-tri-t-butyl-cyclohexa-2,5-dienone and its thermal, photo-, and acid-catalyzed decomposition
作者:Gouki Fukata、Naoya Sakamoto、Masashi Tashiro
DOI:10.1039/p19820002841
日期:——
When the thermolysis was carried out with very low reagent concentrations, 5-cyano-2,4-di-t-butylcyclopenta-2,4-dienone (23), in addition to the phenol (17), was obtained. The compound (23) was also obtained by thermolysis of (3) in boiling acetic anhydride and in boiling toluene containing acetic anhydride. The reaction pathway for the formation of compounds (17), (22), and (23) on thermolysis of the
由4-溴-2,4,6-三叔丁基环己-2,5-二烯酮(1)制备4-叠氮基-2,4,6-三叔丁基环己-2,5-二烯酮(3) )和叠氮化钠的描述。用浓硫酸处理(3)得到2,6-二叔丁基对苯醌(7),产率为75%,而在–10°C的氯仿溶液中反应,则得到三叔丁基ze嗪酮( 5)和3,5-二叔丁基-邻苯醌(8)。将(3)在苯中光解,得到2,4-二叔丁基环戊-2,4-二烯酮(11),将其分离为二聚体(12)。(3)在沸腾的甲苯中热解得到6-氨基-2,4-二叔丁基苯酚(17),2,4,6,8-四叔丁基-1 H-苯恶嗪-1-酮(21 )和2-氰基9,9a-二氢-3,5,7,9a-四叔丁基环戊[[ b ] [1,4]苯并嗪-1(3a H)(一)(22)的产率分别为15,15和48%。当以非常低的试剂浓度进行热解时,除了苯酚(17)之外,还获得了5-氰基-2,4-二叔丁基环戊-2,4-二烯酮(23)。化合物(2