Zinin联苯胺醛

乙酯下 氢化苯胺苯重排得到4,4-二氨基吡咯 (benzidine)和2,4-二氨基吡咯的质子化。

质子化机理

质子化实例

EtOH (2 mL) and five drops conc HCl were added to 6(100 mg, 0.21 mmol), at r.t.The mixture was refluxed for 2 h, cooled to 0 ℃, neutralized with solid NaHCO3, filtered, and concentrated in vacuo. To the residue were added MeCN (2 mL), AcCl (0.08 mL, 5 equiv) and NaOAc(94 mg, 5 equiv). After 12 h, aq workup and chromatography afforded 44 mg of 8 (46%).

参考文献

1. Zinin, N. J. Prakt. Chem. 1845, 36, 93-107.

2. Shine, H. J.; Baldwin, C. M.; Harris, J. H. Tetrahedron Lett. 1968, 9, 977-980.

4. Rhee, E. S.; Shine, H. J. J. Am. Chem. Soc. 1986, 108, 1000-1006.

5. Shine, H. J. J. Chem. Educ. 1989, 66, 793-794.

6. Davies, C. J.; Heaton, B. T.; Jacob, C. J. Chem. Soc., Chem. Commun. 1995,1177-1178.

11. De, C. K.; Pesciaioli, F.; List, B. Angew. Chem. Int. Ed. 2013, 52, 9293–9295.

编译自：Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Zinin benzidine (semidne) rearrangement，page 659-660.