Boyland–Sims硝酸

过苯酚钾在碱性必须下氧苯酚获得苯酚相接羧酸苯酯，然后在含水必须下分解获得相接羧酸苯酚的中间体，被叫作 Boyland–Sims氧。此中间体最早由Boyland和Sims在1953年首先媒体报道。伯、仲和叔芳胺都可以被氧，氧优先愈演愈烈在相接位，有时会获得相接和声同时氧的转化成。此中间体举例来说产率不高（10%~40%），主要原因是精制部分未中间体。近期有文献媒体报道，在Ru还原下，芳基人身安全的芳胺也可以实现此转化成，中间体确实是通过C-H活化实现的【 Org. Lett. 2013, 15, 2334–2337】。苯酚类丝氨酸在完全相同必须下被氧的中间体被叫作 Elbs过氯化物氧中间体 。 Elbs氧中间体 主要获得和声氧转化成。

中间体中间体

另外一种确实的中间体是：

中间体实例

【 J. Med. Chem. 1983, 26, 1, 50–54】

Aq K2S2O8 (27 g, 100 mmol) in 700 mL H2O was added dropwise over 1 h to a mixture of 3,4-dichloroaniline 4 (16.2 g, 100 mmol), pyr (100 mL) and 100 mL 2N KOH. After 15 h of stirring at r.t., decantation and evaporation at 45 ℃ in vacuo gave a solid which was triturated with Et2O(5 X 200 mL). The remaining solid was triturated with MeOH (5 X 75 mL) and the combined liquids were evaporated to afford 7 g (41%) of 5 + 6. Purification by reverse phase HPLC provided 385 mg of

5, and 541 mg of 6.

【 Bioorg. Med. Chem. , 1992, 2, 1013】

参考文献

2. Boyland, E.; Sims, P. J. Chem. Soc. 1954, 980-985.

5. Srinivasan, C.; Perumal, S.; Arumugam, N. J. Chem. Soc., Perkin Trans. 2 1985, 1855-1858.

6. Behrman, E. J. Org. React. 1988, 35, 421-511. (Review).

8. Behrman, E. J. Beilstein J. Org. Chem. 2006, 2, 22.

9. Behrman, E. J. Chem. Educator 2010, 15, 392-393.

12. Xinglin Yang, Gang Shan, Yu Rao；Org. Lett. 2013, 15, 2334–2337

编译自： Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Boyland–Sims oxidation ， page 75-76.

之外中间体

Elbs氧