Synthesis of sterically encumbered 2,4-bis-m-terphenyl-1,3-dichloro-2,4-cyclo-dipnictadiazanes [m-TerNPnCl]2, (Pn = P, As)
作者:Fabian Reiß、Axel Schulz、Alexander Villinger、Nico Weding
DOI:10.1039/c0dt00700e
日期:——
The reaction of m-terphenyl amine (2,6-bis-(2,4,6-trimethylphenyl)aniline, m-Ter = m-terphenyl = 2,6-bis-(2,4,6-trimethylphenyl)) and ECl3 (E = P, As) in the presence of different bases (Et3N, n-BuLi, LDA, DBU) and under different reaction conditions was studied. The reaction with excess Et3N yielded m-Ter–N(H)–AsCl2 for E = As, while for E = P m-Ter–N(PCl2)2 was formed. m-Ter–N(H)–ECl2 was obtained in the reaction of m-terphenyl amine with n-BuLi and ECl3 for E = As and P. Further treatment of m-Ter–N(H)–PCl2 with Et3N led to the formation of 1,3-dichloro-cyclo-1,3-diphospha-2,4-diazane, a synthesis protocol which cannot be applied to the analogous arsenic species. 1,3-dichloro-cyclo-1,3-diarsa-2,4-diazane was isolated when DBU was added to m-Ter–N(H)–AsCl2 at low temperature (−80 °C).
研究了在不同碱(Et3N、n-BuLi、LDA、DBU)存在下和不同反应条件下,间三联苯胺(2,6-双(2,4,6-三甲基苯基)苯胺,m-Ter = m-三联苯 = 2,6-双(2,4,6-三甲基苯基))和ECl3(E = P,As)的反应。以过量Et3N为碱时,E = As 得到 m-Ter–N(H)–AsCl2,而 E = P 得到 m-Ter–N(PCl2)2。在 n-BuLi 和 ECl3 作用下的 m-terphenyl 胺反应中,E = As 和 P 得到了 m-Ter–N(H)–ECl2。进一步用 Et3N 处理 m-Ter–N(H)–PCl2 形成 1,3-二氯环-1,3-二膦-2,4-二氮烷,这个合成方案不能应用于类似的砷衍生物。在-80°C时,将DBU加入到m-Ter–N(H)–AsCl2中,分离得到1,3-二氯环-1,3-二砷-2,4-二氮烷。