Synthesis of Diazoquinones and Azidophenols via Diazo‐Transfer Reaction of Phenols
Synthesis of Diazoquinones and Azidophenols via Diazo‐Transfer Reaction of Phenols
复制标题
通过苯酚的重氮转移反应合成重氮醌和叠氮酚
DOI：
10.1002/ejoc.202200307
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发表时间：
2022
影响因子：
2.8
通讯作者：
Okauchi Tatsuo
中科院分区：
文献类型：
--
作者：
Kitamura Mitsuru;Eto Takashi;Konai Kazushige;Takahashi Shuhei;Shimooka Hirokazu;Okauchi Tatsuo
描述了第一个有效的酚类重氮转移反应。使用 2-叠氮基-1,3-双(2,6-二异丙基苯基)咪唑六氟磷酸盐 (IPrAP,2-PF6) 进行重氮转移反应，以苯酚为原料，高收率地制备了邻醌二叠氮化物（重氮醌），这是一种安全稳定的化合物。 结晶的。该反应在碱存在下在甲醇中有效地进行。被给电子基团取代的酚类比那些被吸电子基团取代的酚类反应更顺利。以iPr2NH为碱，通过IPrAP对活性酚进行重氮化，以N,N-二甲基-4-氨基吡啶(DMAP)对低活性酚进行重氮化。此外，形成的重氮醌与叠氮化钠在2-甲氧基乙醇中反应，以高产率得到相应的叠氮苯酚。
The first efficient diazo‐transfer reaction of phenols is described.o‐Quinone diazides (diazoquinones) were prepared from phenols in high yields by the diazo‐transfer reaction using 2‐azido‐1,3‐bis(2,6‐diisopropylphenyl)imidazolium hexafluorophosphate (IPrAP,2‐PF6), which is a safe and stable crystalline. The reaction efficiently proceeded in methanol in the presence of a base. Phenols substituted with electron‐donating groups reacted more smoothly than those having electron withdrawing groups. Reactive phenols were diazotized by IPrAP withiPr2NH as a base, and low reactive phenols were diazotized withN,N‐dimethyl‐4‐aminopyridine (DMAP). Furthermore, the formed diazoquinones reacted with sodium azide in 2‐methoxyethanol and afforded the corresponding azidophenol in high yields.