高等有機(jī)化學(xué)反應(yīng)機(jī)理省公開(kāi)課一等獎(jiǎng)全國(guó)示范課微課金獎(jiǎng)?wù)n件

高等有機(jī)化學(xué)——反應(yīng)機(jī)理主講教師:劉培念1/103羊群效應(yīng)地獄里發(fā)覺(jué)石油了；群眾眼睛不是血亮；毛毛蟲(chóng)習(xí)慣；盲從與理性；尋找好領(lǐng)頭羊；不走尋常路；自己創(chuàng)造未來(lái)；2/103碳正離子重排反應(yīng)3/103碳正離子1，5-負(fù)氫遷移4/103碳正離子1，2-遷移1，2-遷移與離去基團(tuán)離去是協(xié)同作用XX5/103Beckmann重排6/103練習(xí)7/1038/103Pinacol重排9/103練習(xí)10/10311/103Ph-重排加成——消除機(jī)理：12/103C(sp3)-X取代與β消除反應(yīng)經(jīng)過(guò)SN1與SN2機(jī)理取代反應(yīng)SN1機(jī)理：13/103酸性條件下SN1機(jī)理反應(yīng)14/103練習(xí)15/103酸性條件下SN2機(jī)理反應(yīng)16/10317/103那個(gè)機(jī)理更合理？18/103對(duì)雜原子取代反應(yīng)19/103一個(gè)特例(R,R)(R,R)(S,S)20/103經(jīng)過(guò)E1機(jī)理進(jìn)行β消除反應(yīng)21/10322/103練習(xí)23/10324/103對(duì)親核性C=C親電加成反應(yīng)（烷基或雜原子取代烯烴）（與N,O相連烯烴尤其活潑）（X：無(wú)機(jī)酸、有機(jī)酸、醇、水）25/103范例(Markovnikov’srule)Markovnikov’sruleissimplyanapplicationoftheHammondpostulate:thefasterreactionistheonethatleadstotheintermediatelowerinenergy.26/103練習(xí)27/10328/103C=Cπ鍵與含有孤對(duì)電子親電性雜原子反應(yīng)（X為I,Br時(shí)較穩(wěn)定）（X為Cl時(shí)較穩(wěn)定）29/103練習(xí)30/10331/10332/103親核性C=Cπ鍵取代反應(yīng)親電性苯環(huán)取代反應(yīng)（與HOCOOH類似）33/103苯環(huán)取代基效應(yīng)34/103苯環(huán)取代基效應(yīng)35/10336/10337/10338/103苯胺經(jīng)過(guò)苯重氮鹽取代反應(yīng)39/103苯重氮鹽還原（SRN1機(jī)理）40/103苯重氮鹽與銅(I)化合物反應(yīng)（SRN1機(jī)理）41/103苯重氮鹽與水、BF4-反應(yīng)BecauseneitherH2OnorBF4-areoxidizableenoughtotransferanelectrontothearyldiazoniumion,onlySN1mechanismsarereasonableforthesereactions.42/10343/103Sakuraireaction44/103對(duì)親電性π鍵親核加成與取代反應(yīng)雜原子親核試劑反應(yīng)：45/10346/10347/103酮在酸性或堿性條件下改變反應(yīng)48/103酮還原胺化反應(yīng)49/103對(duì)親電性π鍵親核加成與取代反應(yīng)碳原子親核試劑反應(yīng)：（Robinson閉環(huán)反應(yīng)）50/10351/103Mannich反應(yīng)52/103Mannich反應(yīng)另兩種可能機(jī)理？53/103Mukayama醛醇反應(yīng)54/103Summary55/103Summary56/103第四章周環(huán)反應(yīng)57/1031、基礎(chǔ)知識(shí)

Apericyclicreactionisareactioninwhichbondsareformedorbrokenattheterminiofoneormoreconjugatedsystems.Theelectronsmovearoundinacircle,allbondsaremadeandbrokensimultaneously,andnointermediatesintervene.TypicalreactionsRegioselectivityStereoselectivityStereospecificity58/1034.1.1ClassesofPericyclicReactionsElectrocyclicreactions(ringopeningsorringclosings),CycloadditionsSigmatropicrearrangementsEnereactions.59/103Electrocyclicreactions60/103Cycloadditions61/103CheletropicreactionsCycloadditions62/103Sigmatropicrearrangements63/103Sigmatropicrearrangements64/103Sigmatropicrearrangements65/103EneReaction66/103四種周環(huán)反應(yīng)總結(jié)67/10368/103立體專一性69/103PolyeneMOsWoodward–Hoffmannrules70/103PolyeneMOs71/103PolyeneMOs72/103PolyeneMOs73/1032、電環(huán)化反應(yīng)2.1、經(jīng)典反應(yīng)74/1032.1、經(jīng)典反應(yīng)75/1032.1、經(jīng)典反應(yīng)76/1032.1、經(jīng)典反應(yīng)77/103練習(xí)4.178/1032.1、經(jīng)典反應(yīng)79/1032.1、Favorskiirearrangement80/1032.1、Favorskiirearrangement81/10382/103練習(xí)83/10384/10385/10386/103練習(xí)87/10388/10389/1034.2.2Stereospecificity90/10391/1031,3,5-hexatrienes92/10393/103偶——熱——順奇——熱——反偶——光——反奇——光——順94/103TheWoodward–Hoffmannrulesapplyonlytoconcerted,pericyclicreactions.AreactioncanbeforcedtoproceedthroughthehigherenergyTSifthelowerenergyoneisraisedprohibitivelyhighinenergybygeometricconstraints.95/10396/103