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β-酮酯和重氮鹽在堿或酸催化下制備腙的反應。此反應最早由Japp和Klingemann在1887年報道。此反應條件溫和,反應液接近中性反應。研究發現,用醋酸鈉預先處理強酸重氮鹽,可大大提高反應收率。
反應機理
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反應實例
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【Heterocycles 2000, 53, 665-673】
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【Synth. Commun. 2004, 34, 1791-1799】
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【J. Am. Chem. Soc., 2004, 126, 3534】
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【J. Org. Chem., 2005, 70, 8385】
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【Tetrahedron Lett. 2008, 49, 2835-2838】
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【Tetrahedron Lett. 2013, 53, 4507-4509】
相關文獻
1. (a) Japp, F. R.; Klingemann, F. Ber. 1887, 20, 2942-2944. (b) Japp, F. R.; Klingemann, F. Ber. 1887, 21, 2934-2936. (c) Japp, F. R.; Klingemann, F. Ber. 1887, 20, 3398-3401. (d) Japp, F. R.; Klingemann, F. Ann. 1888, 247, 190-225. (e) Japp, F. R.; Klingemann, F. J. Chem. Soc. 1888, 53, 519-544.
2. Phillips, R. R. Org. React. 1959; 10, 143-178. (Review).
3. Loubinoux, B.; Sinnes, J.-L.; O’Sullivan, A. C.; Winkler, T. J. Org. Chem. 1995, 60, 953-959.
4. Pete, B.; Bitter, I.; Harsanyi, K.; Toke, L. Heterocycles 2000, 53, 665-673.
5. Atlan, V.; Kaim, L. E.; Supiot, C. Chem. Commun. 2000, 1385-1386.
6. Dubash, N. P.; Mangu, N. K.; Satyam, A. Synth. Commun. 2004, 34, 1791-1799.
7. He, W.; Zhang, B.-L.; Li, Z.-J.; Zhang, S.-Y. Synth. Commun. 2005, 35, 1359-1368.
8. Li, J. Japp–Klingemann hydrazone synthesis. In Name Reactions for Functional Group Transformations; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2007, pp 630-634. (Review).
9. Chen, Y.; Shibata, M.; Rajeswaran, M.; Srikrishnan, T.; Dugar, S.; Pandey, R. K. Tetrahedron Lett. 2007, 48, 2353-2356.
10. Pete, B. Tetrahedron Lett. 2008, 49, 2835-2838.
11. Frohberg, P.; Schulze, I.; Donner, C.; Krauth, F. Tetrahedron Lett. 2013, 53, 4507-4509.
參考資料
一、Name Reactions (A Collection of Detailed Reaction Mechanisms), Jie Jack Li, Japp–Klingemann hydrazone synthesis,page 331-332.
二、Comprehensive Organic Name Reactions and Reagents, by Zerong Wang,1552-1556.
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