经典有机化学反应机理大全ppt课件

1、重要的有机反应机理11Arndt-Eistert反应（重氮甲烷与酰氯作用形成 -重氮酮，在Ag离子催化下酰基碳烯 重排得到烯酮。烯酮水解得到多一个碳的羧酸）RCOOHRCOClRCOCHN2RCH2COOHSOCl2CH2N2Ag2OwaterRCOCHN2ROH/Ag2ORCH2COORNH3/Ag2ORCH2CONH22反应机理CH2N2RClOH2C N N+ROCH2N NROCHN N-重氮酮 Ag2OROCHN NROCHRCHC O碳烯 烯酮RCH2COOHRCH2COORRCH2CONH2RCHC OROHH2ONH332Arbuzov反应（亚磷酸酯在卤代烷烃作用下异构重排，生

2、成烷基磷酸酯） (EtO)3P+CH3IrefluxEtOPOEtOCH3or(EtO)3P+BrOEtOrefluxEtOPOEtOOEtO反应机理 OPEtOEtOEtR XOPEtOEtOEtRX-EtXEtOPROEtO43Backman重排 （圬在浓硫酸、PCl5等酸性试剂作用下生成酰胺）PhC6H4OCH3-pNHOPhHNC6H4OCH3-pOPCl5-10oC反应机理NRROHH+NRROH2-H2ONRRR C N RH2ONROH2R-H+NROHRHNROR5 4Baeyer-Villiger氧化（醛或酮被过氧化物氧化得到酯或内酯）反应机理RRORCO3HROORRROR

3、CO3HROORRROHOOOROHRRH+B-+HORO烷基转移顺序：叔烷基仲烷基苯基正烷基甲基65. Bamford-Stevens反应（醛，酮的对甲苯磺酰肼衍生物在碱催化下生成烯烃）反应机理R2HCR1NTsHNRRR1RLiR2HCR1NTsHN2RLiCR1N N TsRR-Ts-C CR1N NRRRRR1LiH2ORRR1H76Benzidine（联苯胺）重排 （氢化偶氮苯与强酸共热，重排为联苯胺）HNHNHClheatNH2H2N反应机理HNHNHClheatNH2H2NH2NNH2HHNH2H2N-2H+87.Benzilic acid（二苯羟乙酸）重排（邻二酮化合物在强碱作

4、用下生成二苯羟乙酸盐）PhPhOOKOHPhPhCOOKHO反应机理PhPhOOOH-PhPhCOOKHOHOOPhOPhHOOPhPhOH+98.Benzoin（安息香）缩合（芳香醛或不含-氢 的脂肪醛在KCN或NaCN的水-乙醇溶液中短时间加热，发生双分子缩合得到-羟基酮 ）PhHO2-CN, heatH2O, EtOHPhOPhOHH反应机理PhHOPhOPhOHHCN+HPhCNOPh CCNOHPh COCNHOHPhPhOCNOHPhHPhOCNOHPhH-CN109.Birch还原（将芳香化合物还原为脂肪族化合物，可得到1，4-二氢环己二烯衍生物）GNa, NH3 (liquid

5、)EtOHGG= COO-, COOR, COR, CONR2, CN, Ar, SiR3 etc.Na, NH3 (liquid)EtOHGG=R, NR2, OR etc.反应机理Na + NH3Na+ e-NH3氨溶剂化的电子很活泼R +e-RRHH=RHH-RHHHHRee-EtOHEtOHEtOH1110.Bouveault-Blanc反应（酯在钠-醇体系中先还原成醛，再进一步还原为伯醇）RCOORNaEtOHRCH2OH反应机理RCH2OHRORONaROROEtOHROROHNaROROHEtOHRHOORHRCHONaRHOEtOHRHOHNaRHOHEtOHEtOHEtO12

6、11.Brown硼氢化反应（烯烃或炔烃与硼烷加成所生成的有机硼烷碱性氧化得到醇或醛地反应）RROH1) R2BH2) H2O2, NaOH反应机理RROHHBRRRHBRRanti-Malkovnicovsyn-additionRHBRRO OHRHBOOHRRROBRR-OOHROBOROR-OH+ B(OH)31312.Carroll 重排（碱催化下的烯丙基醇和-酮酯转化为-酮羰基烯烃）OHR1R2OOOR1+baseR1R1O+ R2OH + CO2OHR1R2OOOR1baseR1R1OOR1R1OR1R1OR2OOOR1R1OObaseOOOR1R1anion promotedCla

7、isen reactionOOOR1R1R1R1O+ CO2H+反应机理1413. Chugaev 反应（醇与二硫化碳及KOH生成磺原酸盐，再甲基化得到磺原酸甲酯，加热分解为烯烃）OH1) CS2, NaOH2)MeI or Me2SO4OSS250oC+反应机理ROH + CS2 + NaOHROSSNaMeIROSS+ NaICHC O CSSRCCHS COSRheatRSSHOCOS + RSH+1514. Claisen 缩合（含-H的酯在碱作用下得到 酮酯）OEtOOEtO+baseOOEtO+ EtOH反应机理CH2OEtOOEtOOOEtO+ EtOHHH2COEtOH2COE

8、tOOOEtOOEt-EtO-EtO1615.Claisen重排（酚或烯醇的烯丙醚加热至200oC，烯丙基由氧原子迁移到碳原子，生成C-烯丙基酚或C-烯丙基酮/醛）OheatOHOOheat反应机理OOHOHheatheatOH3CCH3CH3H2COH3CH3CCH3OHH3CCH3OH1716.Cope重排（1，5-二烯烃在加热下3，3 迁移）300oCHOOheat反应机理PhPhPhPhPhPh1817.Cope消除（叔胺的N-氧衍生物在加热下消除生成烯烃）HN(CH3)2Oheat+ HONMe2heatR+ HONMe2N(CH3)2HRON(CH3)2OHR-+反应机理1918.

9、 Corey-Chaykousky反应（硫叶立德与亲电物种如羰基，烯烃，亚胺，或硫碳基生成相应环化物）反应机理SCH2H3CH3CO(1) DMSYH3CSCH3CH2(2)RR1X(1) or (2)XRR1X= O, CH2, NR2, S, CHCOR3,CHCO2R3, CHCONR2, CHCNH3CSCH2OH3CRR1OH3CSOROH3CR1H3CSCH3OOR1R+2019.Curtius重排（酰基叠氮化合物受热脱氮重排得到异氰酸酯，进一步水解，醇解和胺解生成胺，氨基甲酸酯和取代脲）NCH3PhCOOHH3CCOOH3CCOO1)PN3OPhOPhO, 80oC2) MeOH

10、NCH3PhNH2H3CCOOH3CCOOPhCOOHH3CCH2CH31) SOCl2, Py2) NaN3, xylenePhNH2H3CCH2CH321反应机理RClORNHOROONH2OEtONaN3HNO2NaN3RN N NORNCO+ N2RNCO+ H2ORNOHOHRNH2+ ROHRNOROH2220. Darzens反应（醛酮在碱作用下与 卤代酸酯反应生成，-环氧酯） OOEtClO+baseOH3CPhCOOEt反应机理OEtClObaseORRCOOEtOEtClOOEtClORRO+RORCOOEtCl-Cl-23应用：在羰基碳原子上增长一个碳的醛ORRCOOEt

11、H+ORRCOOHH-CO2-H+RRHOHRCHOR2421.Dieckmann缩合（含-氢的酯缩合生成五元，六元环化合物）EtOOCCOOEtNa or NaOEtOCOOEtEtOOCCOOEtNa or NaOEtOCOOEtCOOEtOEtOCOOEtEtOO+2EtO-COOEtOEtOCOOEtEtOOCOOEtCOOEtOO25反应机理COOEtCOOEtbaseCOOEtOEtOOOHHCOOEt-EtO-OHEtOOC-H+OCOOEtH+OHHOOC-CO2O2622. Diels-Alder反应（共轭二烯与亲二烯体发生环加成得到六元环，反应具有立体专一性）反应机理+Ts

12、MeOOCCOOMe+COOMeHHMeOOCCOOMeCOOMeCOOMeHHCOOMe2723.Enamine（烯胺）反应（二级胺与具有-H的醛，酮发生反应）CHCONHRR+CHCOHNRRN RR反应机理OH3C+NHNH3CBrNH3CH3O+OH3C2824.Eschweiler-Clark反应（将伯胺，仲胺和甲醛及甲酸还原性甲基化制备叔胺）NH2HCHOHCOOH, 95oCNOOONH2HCHOHCOOHNOOOp-ClPhPhOHNH2HCHOHCOOHp-ClPhPhOHN29反应机理RNH2OHH+RNHOHRNHCOOHRNHCH2RNHCHOOHRNHCH3RNHCH

13、3OHH+RNOHCH3H+RNCH3HCOOHRNCH3CH3+ CO2 + H+ orNH2HCHOHCOOHNCH2NH2ONOH3025. Favorskii重排（ -卤代（Cl or Br）酮在强碱（NaOH, NaOEt or NaNH2）作用下重排得到羧酸，酯或酰胺的反应）OClCOOCH3NaOMe反应机理RRXORO-RRXOHRHROHRHRO-ORHHOORRRRCOORRorRCOORR3126.Hantzsch吡啶反应（氨或胺与-丁酮酸酯及其衍生物在醛存在下缩合得到吡啶类化合物）OCOOEt2+ HCHO + NH3NHEtOOCCOOEtH3CCH3NEtOOCCO

14、OEtH3CCH31) NaOH, H2O2) CaO, heatNH3CCH332反应机理EtOOCNH2H3CCH3ORCOOEtNH2RCOOEtEtOOCHH3CCH3ONH2H3COCH3COOEtREtOOCNHOHCH3COOHHEtOOCH3CRNHEtOOCCOOEtH3CCH3RNEtOOCCOOEtH3CCH3R3327.Hofmann消除（季胺碱热分解，得到双键连接烷基最少的烯烃）NHMeI-HINH3CCH3IAg2ONH3CCH3HOheatNH3CCH3MeINH3CCH3CH3IAg2O+Me3I反应机理HCH3HNMe3BrAg2OH2OHCH3HNMe3HO

15、heat-NMe3-H2OCH3H3428. Horner-Wadsworth-Rmmons反应（含稳定碳负离子的磷酸酯在强碱作用下和醛，酮反应得到烯烃化合物）OOOMeOPOOMeH2COMeOMeLiOOOP(OMe)3OOOHCOOEti-Pr(PhO)2PO+ PhCHONaH0oCi-PrCOOEtPhZ : E=99:135反应机理COOEtR2(R1O)2PO+ RCHOOEtOOCRR2H(R1O)2POerythroOEtOOCHR2R(R1O)2POthreoOEtOOCRR2(R1O)2POHOEtOOCHR2(R1O)2PORR2COOEtRCOOEtR2RZE3629

16、.Hoffman 重排（酰胺在卤素，强碱作用下降低一个碳原子得到伯胺）NFNH2OBr2KOHNNH2F反应机理RNH2ONa+-OBrRNHBrOOH-RNOBrRNCORNCOH2ORHNOHORNH2ROHRHNORO3730.Hunsdiecker反应（干燥脂肪酸银盐和卤素在无水溶剂中失去CO2生成卤代烷烃和AgX）COOAgBr2 / heatBr+ CO2 + AgBr反应机理ROAgO+ Br2ROBrOROO+BrROOR+ CO2R+ROBrORBr +ROO3831.Knoevenagel缩合（胺或其他碱的存在下，醛，酮与含活泼亚甲基的化合物缩合，生成,-不饱和酯）CHOO

17、MeOMeEtOOCCOOEt+piperidineOMeOMeCOOEt39反应机理ROOCCOORbaseROOCCOOROC COHCOORCOORH+C COHHCOORCOOR-CO2, OH-COOHC COHHCOOHCOOC COHHCOOHCOOHH2ObaseONH+C NC NOH+EtOOCCOOEtNCOORCOORH-NHCOORCOOR4032.Mannich-Eschenmoser反应（一分子甲醛，一分子仲胺和一分子含有 活泼氢的羰基化合物在铵盐这样的弱酸催化下缩合，在羰基化合物的 碳原子上引入一个氨甲基）CHOCHOOCOOHCOOH+ MeNH2+pH=5H

18、CNMeCHCHCOOHCHCOOHOH2CH2CR H + HCHO+HNR CH2N-CO2HCNMeCHCH2CH2OH2CH2C41反应机理NH2ClCH2O+HN+Cl+H2C OHHN+H2C OHNOHH-H2ON CH2PhCH3OPhCH2OHNH2CPhCH2OH+PhON4233. Michael加成（碳负离子与,-不饱和羰基化合物发生1，4-亲核加成）OEtOCH2(COOEt)2NaOEtOEtOCOOEtEtOOC反应机理CH2(COOEt)2+CH(COOEt)2+ EtOH(EtOOC)2CH+CH3OCH3OCOOEtEtOOCEtOHCH3OCOOEtEtO

19、OCHCH3OCOOEtEtOOCOEt43Michael加成后分子内发生Claisen缩合可得到DimedoneCH3OCOOEtEtOOCOEtOEtOOCCH2OOEt-EtOOCOO1) KOH2) H+OOOEt4434.Mitsunobu反应（醇的取代和构型转化）Ph3P+ROOCN NCOOR + ROH + H-NuPh3P O+RCOONHNHCOOR + R-NuOHDEAD, Ph3PPhH, PhCOOHOOCPhBnOC14H29OHDEAD, Ph3PphtalimideBnOC14H29PthN-BnOC14H29NH2N2H445反应机理Ph3P:EtOOCN

20、NCOOEtPh3P OEtCOONHNHCOOEtEtOOCN NCOOEtPPh3H-NuEtOOCN NHCOOEtPPh3NuEtOOCN NHCOOEtPPh3NuOH+O PPh3NuO PPh3NuNu+4635.Mukaiyama-Carreira醇醛反应(将一分子羰基化合物预先制成更活泼的烯醇硅醚，在Lewis催化下与另一分子羰基化合物进行交叉Aldol反应）O1) LDA2) TMSClOTMSOTMSHOTiCl4OOTiClClClH2OO反应机理R3OR1TiCl4H2OR2R1OSi(CH3)3R3+OR5R4SiMe3R2OR4R5ClTiCl3-TMSClR5R

21、3OCl3TiR1R2R4R4OHR5R2R1R3O4736.Nef反应（从硝基化合物制备醛，酮）NO2NaOHNOOH2SO4CHO反应机理HNRROO_+:BNRROO-+H+NRROHOH+H2O-H+RHORNOHOH-H2ON ORHORORR4837. Peterson反应（-羰基负离子与羰基化合物反应生成烯基化合物）Me3SiMgClPhCHOOPhTMSH2OPhHOTMSPhSiR3RCO3HOSiR3H3O+OHOHSiR3OHO反应机理OPhTMSH2OPhHOTMSH3O+ORTMSPhRLiRRbase(Na,K)OPhRTMSMe3SiPhROsyn elimPhR

22、PhH2OTMSRH2OPhHOTMSRanti elimPhR4938.Perkin反应（芳香醛与羧酸酐的反应）HO+ (RCH2CO)2ObaseArHCOOHR+RCH2COOH反应机理RH2COOH2CORbaseRHCOOH2CORArCHOArOHRHOOORH2OArHCOOHR+RCH2COOH5039.Pinacol反应（1，2-二醇用酸处理得到醛或酮）HOPhPhMeOHMeH2SO4MeOMePhPh反应机理OR1R3R2R4BF3R3OR1R2R4R2R1OHR3OHR4H+R2R1OHR3OH2R4R2R1OHR3R4R2OHR1R3R4-H+R2OR1R3R4514

23、0.Smiles重排NO2YCCZNO2ZCCYY=S, SO, SO2, O, COO etc.Z=OH, NH2, NHR, CONH2, CONHR, SH, and CH3s conjugate baseO2SOHNO2OH-SO2ONO2反应机理O2SOHNO2OH-SO2ONO2O2SONO2SNArOO2SNO2Meisenheimer complex5241.Sommelet重排（苯甲基三甲基季铵盐用钠胺处理得到苯甲基三级胺）NMe3NaNH2CH3NMe2反应机理NaNH2CH2N(CH3)3H3CCHN(CH3)3H3CCH2N(CH3)2H3CCH2CH2N(CH3)2H

24、3CHH3CCH3CH2N(CH3)25342.Stevens重排（强碱作用下季铵盐中烃基从N原子迁移到相邻C负离子的反应，锍盐也可发生此反应）H3CNCH3RRH2CX-NaOEtH3CNCH3RRHCX-RRNCH3CH3HNMe2PhNaOEtNMe2PhNMe2PhSCH3PhOCH2CCH2PhNaOEtSCH3PhOCHCCH2PhPhOSCH3Ph54 R为乙酰基，苯甲酰基，苯基等吸电子基；迁移基团R为烯丙基，苄基，取代苯甲基等。迁移基团上有吸电子基时反应速度加快。在Stevens重排中，迁移基团的构型保持不变。NPhOCH2CNaOEtMeMeCH3PhHNPhOCHCMeMeCH3PhHPhONMe2HPhMe5543.Stork烯胺烃基化和酰基化（醛或酮经过烯胺或亚胺的烃基化和酰基化反应）O+NOHTsOHNOCl(CH2)8OEt3NO(CH2)8ONC6H11EtMgBrNC6H11MgBrBrH3O+CHONNOMe1) LDA, 0oC2) Eu, -95oCNNOMeEtO3EtO56反应机理OH+OHNHHONH+H2ON-H2OHN-H+NNRXNRXRNXHONROR+N