Smith Michael B, Guo Lisa Chen, Okeyo Sherrad, Stenzel Jason, Yanella James, LaChapelle Eric
Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, Connecticut 06269-3060, USA.
Org Lett. 2002 Jul 11;4(14):2321-3. doi: 10.1021/ol0259600.
[reaction: see text] Treatment of aniline with n-butyllithium and then trimethyltin chloride gave the tin amide (PhNH-SnMe(3)) in situ. Without isolation of the tin amide, reaction with bromine and workup with aqueous fluoride ion gave p-bromoaniline in 76% yield, with no dibromoaniline or o-bromoaniline. Application of this sequence to 11 different aromatic amines gave selective bromination in 36-91% yields, without formation of dibromides. This constitutes a good general method for the regioselective bromination of aromatic amines.
[反应：见正文] 用正丁基锂处理苯胺，然后加入三甲基氯化锡，原位生成锡酰胺（PhNH-SnMe(3)）。无需分离锡酰胺，与溴反应并用水性氟离子后处理，得到对溴苯胺，产率为76%，无二溴苯胺或邻溴苯胺。将此反应序列应用于11种不同的芳香胺，选择性溴化产率为36 - 91%，不生成二溴化物。这构成了一种用于芳香胺区域选择性溴化的良好通用方法。
