芳香胺的区域选择性一锅法溴化反应。

Regioselective one-pot bromination of aromatic amines.

作者信息

Smith Michael B, Guo Lisa Chen, Okeyo Sherrad, Stenzel Jason, Yanella James, LaChapelle Eric

机构信息

Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, Connecticut 06269-3060, USA.

出版信息

Org Lett. 2002 Jul 11;4(14):2321-3. doi: 10.1021/ol0259600.

DOI:10.1021/ol0259600

PMID:12098237

Abstract

[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.

摘要

[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。