1. Chemistry Department 01 包江胤 郑睿
Rearrange reactions
Chemistry Department 01
包江胤 郑睿

2. 1.Abstract The history is as long as organic compounds
Definition: a reaction that results in a product with a different carbon skeleton from the reactant

3. Classification Nucleophilic rearrangments Free radical rearrangments
Electrophilic rearrangments
Pericyclic reaction

4. Nucleophilic rearrangements

5. Eletrons on the molecular orbitals of the transition state & reactive intermidiate

6. 2.Nucleophilic rearrangements
General rule
1)Process
2)Condition
3)Migrating group
4)Stereochemistry
5)Memory effect

7. 1)Process

8. Classification
1)Carbonium ion
2)Carbonyl
3)Carbene
4)Electron-defect nitrogen
5)Electron-defect oxygen
6)Aromatic series

9. 1)Carbonium ion
(1)Rearrangements in the composition of aldehydes and ketones
(2)Rearrangements of pinacols
(3)Wagner-Meerwein’s rearrangements
(4)Demyanov’s rearrangements
(5)Tiffeneau-Demyanov’s circles expanding
(6)Rearrangements from dienones to phenols
(7)Rearrangements with allyl groups

10. Rearrangements in the composition of aldehydes and ketones

12. 33-36% O.S.Ⅳ，225

13. Rearrangements of pinacols

14. 2)Carbonyl
Benzil-benzilic acid rearrangements
(2)Rearrangements of aldehydes or ketones when catalysised by acid

15. Benzil-Benzilic acid arrangement

16. 3)Carbene
Arndt-fistert synthesis and Wolff rearrangement
(2)Other carbenes’s rearrangement reaction

17. 4)Electron-defect nitrogen
(1)Beckmann’s rearrangement
(2)Hofmann’s rearrangement
(3)Curtius’s rearrangement
(4)Schmidt’s rearrangement
(5)Neber’s rearrangement
(6)Lossen’s rearrangement

18. Beckmann’s rearrangement

19. Hofmann’s rearrangement

20. Curtius’s rearrangement

21. Schmidt’s rearrangement

22. Neber’s rearrangement

23. 5)Electron-defect oxygen
(1)Hydroperoxide rearrangement
(2)Baeyer-Villiger rearrangement

25. 6)Aromatic series
(1)Bamberger rearrangement
(2)Scommelet-hauser rearrangement
(3)Simles rearrangement

26. 3.Free radical rearrangements
1,2 shift
Others
(1)Barton rearrangement
(2)Hofmann-Loffler-Freytag rearrangement

27. Barton’s rearrangement

28. 4.Electrophilic rearrangements
1) Aliphatic rearrangements
(1)Farorskii rearrangements
(2)Grovenatein-Zimmerman rearrangements
(3)Stevens rearrangements
(4)Wittig rearrangements

29. 2)Aromatic series
(1)Fries rearrangement
(2)Aromatic ether rearrangement
(3)Orton rearrangement
(4)N-nitro aromatic amine rearrangement
(5)Fischer-Hepp rearrangement
(6)Hofmann-Martius rearrangement
(7)Diazonamino compounds rearrangement

30. Favorskii’s rearrangements

32. Fries’ rearrangements

33. 5. Pericyclic reaction (1)Electrocyclic reaction (2)σ-bonds shift
(3)Cope rearrangements
(4)Claisen rearrangements
(5)Fischer indole synthesis
(6)Benzdine rearrangements

34. Electrocyclic reaction

36. References 杜汝励，分子重排反应，人民教育出版社，1981年 王其华，有机反应机制导论，高等教育出版社，1991年
李进文，范如霖编译，实用有机化学手册，上海科学技术出版社，1981年
金寄春，重排反应，高等教育出版社，1990
P.Sykes,A Guidebook To Mechanism In Organic Chemistry,Longman,1981