经典有机化学反应机理大全PPT精选文档

1、重要的有机反应机理1Arndt-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/Ag2ORCH2CONH2反应机理CH2N2RClOH2C N N+ROCH2N NROCHN N-重氮酮 Ag2OROCHN NROCHRCHC O碳烯 烯酮RCH2COOHRCH2COORRCH2CONH2RCHC OROHH2ONH32Arbuzov反应（亚磷酸酯在卤代烷烃作用下异构重排，生成烷基

2、磷酸酯） (EtO)3P+CH3IrefluxEtOPOEtOCH3or(EtO)3P+BrOEtOrefluxEtOPOEtOOEtO反应机理 OPEtOEtOEtRXOPEtOEtOEtRX-EtXEtOPROEtO3Backman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+NROHRHNROR 4Baeyer-Villiger氧化（醛或酮被过氧化物氧化得到酯或内酯）反应机理RRORCO3HROORRRORCO3HRO

3、ORRROHOOOROHRRH+B-+HORO烷基转移顺序：叔烷基仲烷基苯基正烷基甲基5. 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 NRRRRR1LiH2ORRR1H6Benzidine（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+Benzilic acid（二苯羟乙酸）重排（邻二酮化合物在强碱作用下生成二苯羟乙酸盐）

4、PhPhOOKOHPhPhCOOKHO反应机理PhPhOOOH-PhPhCOOKHOHOOPhOPhHOOPhPhOH+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-CNBirch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)EtOHGG= COO-, COO

5、R, 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-EtOHEtOHEtOHBouveault-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RCH2OHRORONaROROEtOHROROHNaROROHEtOHRHOORHRCHONaRHOEtOHRHOHNaRHOHEtOHEtOHEtOBrown硼氢化反应（烯烃或炔烃与硼烷加成所生成的

6、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)3Carroll 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 promotedClaisen reactionOOOR1R1R1R1O+ CO2H+反

7、应机理13. 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+14. Claisen 缩合（含-H的酯在碱作用下得到 酮酯）OEtOOEtO+baseOOEtO+ EtOH反应机理CH2OEtOOEtOOOEtO+ EtOHHH2COEtOH2COEtOOOEtOOEt-EtO-EtOClaisen重排（酚或烯醇的烯丙醚加

8、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OOHOHheatheatOH3CCH3CH3H2COH3CH3CCH3OHH3CCH3OHCope重排（1，5-二烯烃在加热下3，3 迁移）300oCHOOheat反应机理PhPhPhPhPhPhCope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18. 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

9、理SCH2H3CH3CO(1) DMSYH3CSCH3CH2(2)RR1X(1) or (2)XRR1X= O, CH2, NR2, S, CHCOR3,CHCO2R3, CHCONR2, CHCNH3CSCH2OH3CRR1OH3CSOROH3CR1H3CSCH3OOR1R+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) MeOHNCH3PhNH2H3CCOOH3CCOOPhCOOHH3CCH2CH31) SOCl2, Py2) NaN3, xy

10、lenePhNH2H3CCH2CH3反应机理RClORNHOROONH2OEtONaN3HNO2NaN3RN N NORNCO+ N2RNCO+ H2ORNOHOHRNH2+ ROHRNOROH20. 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-应用：在羰基碳原子上增长一个碳的醛ORRCOOEtH+ORRCOOHH-CO2-H+RRHOHRCHORDieckmann缩合（含-氢的酯缩合生成五元，六元环化合物）EtOOCCO

11、OEtNa or NaOEtOCOOEtEtOOCCOOEtNa or NaOEtOCOOEtCOOEtOEtOCOOEtEtOO+2EtO-COOEtOEtOCOOEtEtOOCOOEtCOOEtOO反应机理COOEtCOOEtbaseCOOEtOEtOOOHHCOOEt-EtO-OHEtOOC-H+OCOOEtH+OHHOOC-CO2O22. 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+TsMeOOCCOOMe+COOMeHHMeOOCCOOMeCOOMeCOOMeHHCOOMeEnamine（烯胺）反应（二级胺与具有-H的醛，酮发生反

12、应）CHCONHRR+CHCOHNRRN RR反应机理OH3C+NHNH3CBrNH3CH3O+OH3CEschweiler-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-ClPhPhOHN反应机理RNH2OHH+RNHOHRNHCOOHRNHCH2RNHCHOOHRNHCH3RNHCH3OHH+RNOHCH3H+RNCH3HCOOHRNCH3CH3+ CO2 + H+ orNH2HCHOHCOOHNCH2NH2ONOH25. Favorskii重排（ -

13、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-ORHHOORRRRCOORRorRCOORRHantzsch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 + NH3NHEtOOCCOOEtH3CCH3NEtOOCCOOEtH3CCH31) NaOH, H2O2) CaO, heatNH3CCH3反应机理EtOOCNH2H3CCH3ORCOOEtNH2RCOOEtEtOOCHH3CCH3ONH2H3C

14、OCH3COOEtREtOOCNHOHCH3COOHHEtOOCH3CRNHEtOOCCOOEtH3CCH3RNEtOOCCOOEtH3CCH3RHofmann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HCH3HNMe3BrAg2OH2OHCH3HNMe3HOheat-NMe3-H2OCH3H28. 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）OOOMeOPOOMeH2COMeOMeLi

15、OOOP(OMe)3OOOHCOOEti-Pr(PhO)2PO+ PhCHONaH0oCi-PrCOOEtPhZ : E=99:1反应机理COOEtR2(R1O)2PO+ RCHOOEtOOCRR2H(R1O)2POerythroOEtOOCHR2R(R1O)2POthreoOEtOOCRR2(R1O)2POHOEtOOCHR2(R1O)2PORR2COOEtRCOOEtR2RZEHoffman 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-RNOBrRNCORNCOH2ORHNOHORNH2ROHRHN

16、OROHunsdiecker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 +ROOKnoevenagel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）CHOOMeOMeEtOOCCOOEt+piperidineOMeOMeCOOEt反应机理ROOCCOORbaseROOCCOOROC COHCOORCOORH+C COHHCOORCOOR-CO2, OH-COOHC COHHCOOHCOOC

17、COHHCOOHCOOHH2ObaseONH+C NC NOH+EtOOCCOOEtNCOORCOORH-NHCOORCOORMannich-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=5HCNMeCHCHCOOHCHCOOHOH2CH2CR H + HCHO+HNR CH2N-CO2HCNMeCHCH2CH2OH2CH2C反应机理NH2ClCH2O+HN+Cl+H2C OHHN+H2C OHNOHH-H2ON CH2PhCH3OPhCH

18、2OHNH2CPhCH2OH+PhON33. 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+CH3OCH3OCOOEtEtOOCEtOHCH3OCOOEtEtOOCHCH3OCOOEtEtOOCOEtMichael加成后分子内发生Claisen缩合可得到DimedoneCH3OCOOEtEtOOCOEtOEtOOCCH2OOEt-EtOOCOO1) KOH2) H+OOOEtMitsunobu反应（醇的取代和构型转化

19、）Ph3P+ROOCN NCOOR + ROH + H-NuPh3P O+RCOONHNHCOOR + R-NuOHDEAD, Ph3PPhH, PhCOOHOOCPhBnOC14H29OHDEAD, Ph3PphtalimideBnOC14H29PthN-BnOC14H29NH2N2H4反应机理Ph3P:EtOOCN NCOOEtPh3P OEtCOONHNHCOOEtEtOOCN NCOOEtPPh3H-NuEtOOCN NHCOOEtPPh3NuEtOOCN NHCOOEtPPh3NuOH+O PPh3NuO PPh3NuNu+Mukaiyama-Carreira醇醛反应(将一分子羰基化

20、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-TMSClR5R3OCl3TiR1R2R4R4OHR5R2R1R3ONef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 ORHORORR37. Peterson反应（-羰基负离子与

21、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 elimPhRPhH2OTMSRH2OPhHOTMSRanti elimPhRPerkin反应（芳香醛与羧酸酐的反应）HO+ (RCH2CO)2ObaseArHCOOHR+RCH2COOH反应机理RH2COOH2CORbaseRHCOOH2CORArCHOArOHRHOOORH2OArHCOOHR+RCH2COOH

22、Pinacol反应（1，2-二醇用酸处理得到醛或酮）HOPhPhMeOHMeH2SO4MeOMePhPh反应机理OR1R3R2R4BF3R3OR1R2R4R2R1OHR3OHR4H+R2R1OHR3OH2R4R2R1OHR3R4R2OHR1R3R4-H+R2OR1R3R4Smiles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-SO2ONO2O2SONO2SNArOO2SNO2Me

23、isenheimer complexSommelet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)2H3CHH3CCH3CH2N(CH3)2Stevens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-RRNCH3CH3HNMe2PhNaOEtNMe2PhNMe2PhSCH3PhOCH2CCH2PhNaOEtSCH3PhOCHCCH2PhPhO

24、SCH3Ph 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。NPhOCH2CNaOEtMeMeCH3PhHNPhOCHCMeMeCH3PhHPhONMe2HPhMeStork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, -95oCNNOMeEtO3EtO反应机理OH+OHNHHONH+H2ON-H2OHN-H+NNRXNRXRNXHONROR+