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1、Rearrange reactionsChemistry Department 01包江胤郑睿1.AbstractThe history is as long as organic compoundsDefinition:a reaction that results in a product with a different carbon skeleton from the reactantClassificationNucleophilic rearrangmentsFree radical rearrangmentsElectrophilic rearrangmentsPericycli
2、c reactionNucleophilic rearrangements Eletrons on the molecular orbitals of the transition state&reactive intermidiate 2.Nucleophilic rearrangements General rule 1)Process 2)Condition 3)Migrating group 4)Stereochemistry 5)Memory effect1)Process Classification 1)Carbonium ion 2)Carbonyl 3)Carbene 4)E
3、lectron-defect nitrogen 5)Electron-defect oxygen 6)Aromatic series1)Carbonium ion(1)Rearrangements in the composition of aldehydes and ketones(2)Rearrangements of pinacols(3)Wagner-Meerweins rearrangements(4)Demyanovs rearrangements(5)Tiffeneau-Demyanovs circles expanding(6)Rearrangements from dieno
4、nes to phenols(7)Rearrangements with allyl groups Rearrangements in the composition of aldehydes and ketones 33-36%O.S.，225Rearrangements of pinacols2)Carbonyl(1)Benzil-benzilic acid rearrangements(2)Rearrangements of aldehydes or ketones when catalysised by acidBenzil-Benzilic acid arrangement3)Car
5、bene(1)Arndt-fistert synthesis and Wolff rearrangement(2)Other carbeness rearrangement reaction4)Electron-defect nitrogen(1)Beckmanns rearrangement(2)Hofmanns rearrangement(3)Curtiuss rearrangement(4)Schmidts rearrangement(5)Nebers rearrangement(6)Lossens rearrangementBeckmanns rearrangementHofmanns
6、 rearrangementCurtiuss rearrangementSchmidts rearrangementNebers rearrangement5)Electron-defect oxygen(1)Hydroperoxide rearrangement(2)Baeyer-Villiger rearrangement 6)Aromatic series(1)Bamberger rearrangement(2)Scommelet-hauser rearrangement(3)Simles rearrangement3.Free radical rearrangements1,2 shi
7、ftOthers(1)Barton rearrangement(2)Hofmann-Loffler-Freytag rearrangementBartons rearrangement 4.Electrophilic rearrangements1)Aliphatic rearrangements(1)Farorskii rearrangements(2)Grovenatein-Zimmerman rearrangements(3)Stevens rearrangements(4)Wittig rearrangements2)Aromatic series(1)Fries rearrangem
8、ent(2)Aromatic ether rearrangement(3)Orton rearrangement(4)N-nitro aromatic amine rearrangement(5)Fischer-Hepp rearrangement(6)Hofmann-Martius rearrangement(7)Diazonamino compounds rearrangementFavorskiis rearrangements Fries rearrangements 5.Pericyclic reaction(1)Electrocyclic reaction(2)-bonds shi
9、ft(3)Cope rearrangements(4)Claisen rearrangements(5)Fischer indole synthesis(6)Benzdine rearrangementsElectrocyclic reaction References杜汝励，分子重排反应，人民教育出版社，杜汝励，分子重排反应，人民教育出版社，19811981年年王其华，有机反应机制导论，高等教育出版社，王其华，有机反应机制导论，高等教育出版社，19911991年年李进文，范如霖编译，实用有机化学手册，上海科学技术李进文，范如霖编译，实用有机化学手册，上海科学技术出版社，出版社，19811981年年金寄春，重排反应，高等教育出版社，金寄春，重排反应，高等教育出版社，19901990P.Sykes,A Guidebook To Mechanism In Organic P.Sykes,A Guidebook To Mechanism In Organic Chemistry,Longman,1981Chemistry,Longman,1981