The bisphenol 1 was obtained by reacting the amine hydrochloride 11 with cyanoacetic acid in aqueous sodium hydroxide solution. Thermal rearrangement of 1,5-bis(allyloxyphenyl)formazan (7) failed to give 1. Alkylation of the bis phenol 1 with 1,3-dibromopropane in basic solution under high dilution conditions gave the corresponding allyl-substituted macrocyclic formazan 2a in a very low yield. On the other hand, diazotization of the new bis amine hydrochloride 3a,b with NaNO2 in hydrochloric acid followed by coupling with the appropriate active methylene compounds furnished the corresponding macrocyclic formazans 2a-d. Compounds 3a ,b were obtained by first reacting the K-salt of 12 with the appropriate dihalides to give the corresponding bis acetamides 13 and 14, respectively. Subsequent acid hydrolysis of the latter afforded 3a,b in good yield.
双
酚1是通过将
氨基盐酸盐11与
氰基
乙酸在
水合
氢氧化钠溶液中反应获得的。1,5-双(烯
丙氧基苯基)
氨基
脲(7)的热重排未能生成1。在高稀释条件下,将双
酚1与
1,3-二溴丙烷在碱性溶液中烷基化反应得到相应的烯丙基取代的大环
氨基
脲2a,但产率非常低。另一方面,新双
氨基盐酸盐3a,b在
盐酸中与
亚硝酸钠进行重氮化反应,随后与适当的活性亚甲基化合物偶联,得到了相应的大环
氨基
脲2a-d。化合物3a,b是通过首先将12的K盐与适当的二卤化物反应,分别得到相应的
双乙酰胺13和14,随后对后者进行酸
水解,良好地获得了3a,b。