Stieglitz N-卤代胺重排
N-卤代三芳基叔胺在碱性条件下经由氮宾中间体重排为芳胺的反应。也可以通过氧化得到氮宾后重排。
反应机理
经由氮宾三元环中间体重排得到产物，机理同Hofmann重排。
反应实例
Phenylphenanthridine (3). Amine hydrochloride 1 (2.72 g, 9.28 mmol) in EtOH (75 mL) was treated with 0.926N cold solution of KOCl. After crystals formed, the mixture was shaken for 30 min in ice, water was added. Filtration gave 2.7 g of 2 (100%), mp 102 C (hexane). To the latter (2 g, 6.8 mmol) in 20 mL anhyd Pyr was added an excess of NaOCH3 (exothermic). After 20 h evaporation
in vacuo, trituration of the residue with Et2O and treatment of the extract with dry HCl afforded 3 HCl, mp 107–108 C (from pet ether).
【Pinck LA, J Am Chem Soc, 1937, 59, 8】
N-(diphenylmethylene)aniline (5). To LTA (4.9 g, 10 mmol) in 100 mL PhH was added dropwise under N2 triphenylmethylamine 4 (2.6 g, 10 mmol) in 100 mL PhH. The mixture was refluxed for 1 h. Workup and crystallization from EtOH afforded 2.2 g of 5 (85%), mp 111–112 C.
【Sisti AJ, J Org Chem, 1974, 39, 3932】
编译自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 459.
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