經(jīng)典有機化學反應機理大全

1、重要的有機反應機理1Arndt-Eistert反應（重氮甲烷與酰氯作用形成 -重氮酮，在Ag離子催化下酰基碳烯 重排得到烯酮。烯酮水解得到多一個碳的羧酸）RCOOHRCOClRCOCHN2RCH2COOHSOCl2CH2N2Ag2OwaterRCOCHN2ROH/Ag2ORCH2COORNH3/Ag2ORCH2CONH2反應機理CH2N2RClOH2C N N+ROCH2N NROCHN N-重氮酮 Ag2OROCHN NROCHRCHC O碳烯 烯酮RCH2COOHRCH2COORRCH2CONH2RCHC OROHH2ONH32Arbuzov反應（亞磷酸酯在鹵代烷烴作用下異構重排，生成烷基

2、磷酸酯） (EtO)3P+CH3IrefluxEtOPOEtOCH3or(EtO)3P+BrOEtOrefluxEtOPOEtOOEtO反應機理 OPEtOEtOEtRXOPEtOEtOEtRX-EtXEtOPROEtO3Backman重排 （圬在濃硫酸、PCl5等酸性試劑作用下生成酰胺）PhC6H4OCH3-pNHOPhHNC6H4OCH3-pOPCl5-10oC反應機理NRROHH+NRROH2-H2ONRRR C N RH2ONROH2R-H+NROHRHNROR 4Baeyer-Villiger氧化（醛或酮被過氧化物氧化得到酯或內(nèi)酯）反應機理RRORCO3HROORRRORCO3HRO

3、ORRROHOOOROHRRH+B-+HORO烷基轉移順序：叔烷基仲烷基苯基正烷基甲基5. Bamford-Stevens反應（醛，酮的對甲苯磺酰肼衍生物在堿催化下生成烯烴）反應機理R2HCR1NTsHNRRR1RLiR2HCR1NTsHN2RLiCR1N N TsRR-Ts-C CR1N NRRRRR1LiH2ORRR1H6Benzidine（聯(lián)苯胺）重排 （氫化偶氮苯與強酸共熱，重排為聯(lián)苯胺）HNHNHClheatNH2H2N反應機理HNHNHClheatNH2H2NH2NNH2HHNH2H2N-2H+Benzilic acid（二苯羥乙酸）重排（鄰二酮化合物在強堿作用下生成二苯羥乙酸鹽）

4、PhPhOOKOHPhPhCOOKHO反應機理PhPhOOOH-PhPhCOOKHOHOOPhOPhHOOPhPhOH+Benzoin（安息香）縮合（芳香醛或不含-氫 的脂肪醛在KCN或NaCN的水-乙醇溶液中短時間加熱，發(fā)生雙分子縮合得到-羥基酮 ）PhHO2-CN, heatH2O, EtOHPhOPhOHH反應機理PhHOPhOPhOHHCN+HPhCNOPh CCNOHPh COCNHOHPhPhOCNOHPhHPhOCNOHPhH-CNBirch還原（將芳香化合物還原為脂肪族化合物，可得到1，4-二氫環(huán)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.反應機理Na + NH3Na+ e-NH3氨溶劑化的電子很活潑R +e-RRHH=RHH-RHHHHRee-EtOHEtOHEtOHBouveault-Blanc反應（酯在鈉-醇體系中先還原成醛，再進一步還原為伯醇）RCOORNaEtOHRCH2OH反應機理RCH2OHRORONaROROEtOHROROHNaROROHEtOHRHOORHRCHONaRHOEtOHRHOHNaRHOHEtOHEtOHEtOBrown硼氫化反應（烯烴或炔烴與硼烷加成所生成的

6、有機硼烷堿性氧化得到醇或醛地反應）RROH1) R2BH2) H2O2, NaOH反應機理RROHHBRRRHBRRanti-Malkovnicovsyn-additionRHBRRO OHRHBOOHRRROBRR-OOHROBOROR-OH+ B(OH)3Carroll 重排（堿催化下的烯丙基醇和-酮酯轉化為-酮羰基烯烴）OHR1R2OOOR1+baseR1R1O+ R2OH + CO2OHR1R2OOOR1baseR1R1OOR1R1OR1R1OR2OOOR1R1OObaseOOOR1R1anion promotedClaisen reactionOOOR1R1R1R1O+ CO2H+反

7、應機理13. Chugaev 反應（醇與二硫化碳及KOH生成磺原酸鹽，再甲基化得到磺原酸甲酯，加熱分解為烯烴）OH1) CS2, NaOH2)MeI or Me2SO4OSS250oC+反應機理ROH + CS2 + NaOHROSSNaMeIROSS+ NaICHC O CSSRCCHS COSRheatRSSHOCOS + RSH+14. Claisen 縮合（含-H的酯在堿作用下得到 酮酯）OEtOOEtO+baseOOEtO+ EtOH反應機理CH2OEtOOEtOOOEtO+ EtOHHH2COEtOH2COEtOOOEtOOEt-EtO-EtOClaisen重排（酚或烯醇的烯丙醚加

8、熱至200oC，烯丙基由氧原子遷移到碳原子，生成C-烯丙基酚或C-烯丙基酮/醛）OheatOHOOheat反應機理OOHOHheatheatOH3CCH3CH3H2COH3CH3CCH3OHH3CCH3OHCope重排（1，5-二烯烴在加熱下3，3 遷移）300oCHOOheat反應機理PhPhPhPhPhPhCope消除（叔胺的N-氧衍生物在加熱下消除生成烯烴）HN(CH3)2Oheat+ HONMe2heatR+ HONMe2N(CH3)2HRON(CH3)2OHR-+反應機理18. Corey-Chaykousky反應（硫葉立德與親電物種如羰基，烯烴，亞胺，或硫碳基生成相應環(huán)化物）反應機

9、理SCH2H3CH3CO(1) DMSYH3CSCH3CH2(2)RR1X(1) or (2)XRR1X= O, CH2, NR2, S, CHCOR3,CHCO2R3, CHCONR2, CHCNH3CSCH2OH3CRR1OH3CSOROH3CR1H3CSCH3OOR1R+Curtius重排（?；B氮化合物受熱脫氮重排得到異氰酸酯，進一步水解，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反應機理RClORNHOROONH2OEtONaN3HNO2NaN3RN N NORNCO+ N2RNCO+ H2ORNOHOHRNH2+ ROHRNOROH20. Darzens反應（醛酮在堿作用下與 鹵代酸酯反應生成，-環(huán)氧酯） OOEtClO+baseOH3CPhCOOEt反應機理OEtClObaseORRCOOEtOEtClOOEtClORRO+RORCOOEtCl-Cl-應用：在羰基碳原子上增長一個碳的醛ORRCOOEtH+ORRCOOHH-CO2-H+RRHOHRCHORDieckmann縮合（含-氫的酯縮合生成五元，六元環(huán)化合物）EtOOCCO

11、OEtNa or NaOEtOCOOEtEtOOCCOOEtNa or NaOEtOCOOEtCOOEtOEtOCOOEtEtOO+2EtO-COOEtOEtOCOOEtEtOOCOOEtCOOEtOO反應機理COOEtCOOEtbaseCOOEtOEtOOOHHCOOEt-EtO-OHEtOOC-H+OCOOEtH+OHHOOC-CO2O22. Diels-Alder反應（共軛二烯與親二烯體發(fā)生環(huán)加成得到六元環(huán)，反應具有立體專一性）反應機理+TsMeOOCCOOMe+COOMeHHMeOOCCOOMeCOOMeCOOMeHHCOOMeEnamine（烯胺）反應（二級胺與具有-H的醛，酮發(fā)生反

12、應）CHCONHRR+CHCOHNRRN RR反應機理OH3C+NHNH3CBrNH3CH3O+OH3CEschweiler-Clark反應（將伯胺，仲胺和甲醛及甲酸還原性甲基化制備叔胺）NH2HCHOHCOOH, 95oCNOOONH2HCHOHCOOHNOOOp-ClPhPhOHNH2HCHOHCOOHp-ClPhPhOHN反應機理RNH2OHH+RNHOHRNHCOOHRNHCH2RNHCHOOHRNHCH3RNHCH3OHH+RNOHCH3H+RNCH3HCOOHRNCH3CH3+ CO2 + H+ orNH2HCHOHCOOHNCH2NH2ONOH25. Favorskii重排（ -

13、鹵代（Cl or Br）酮在強堿（NaOH, NaOEt or NaNH2）作用下重排得到羧酸，酯或酰胺的反應）OClCOOCH3NaOMe反應機理RRXORO-RRXOHRHROHRHRO-ORHHOORRRRCOORRorRCOORRHantzsch吡啶反應（氨或胺與-丁酮酸酯及其衍生物在醛存在下縮合得到吡啶類化合物）OCOOEt2+ HCHO + NH3NHEtOOCCOOEtH3CCH3NEtOOCCOOEtH3CCH31) NaOH, H2O2) CaO, heatNH3CCH3反應機理EtOOCNH2H3CCH3ORCOOEtNH2RCOOEtEtOOCHH3CCH3ONH2H3C

14、OCH3COOEtREtOOCNHOHCH3COOHHEtOOCH3CRNHEtOOCCOOEtH3CCH3RNEtOOCCOOEtH3CCH3RHofmann消除（季胺堿熱分解，得到雙鍵連接烷基最少的烯烴）NHMeI-HINH3CCH3IAg2ONH3CCH3HOheatNH3CCH3MeINH3CCH3CH3IAg2O+Me3I反應機理HCH3HNMe3BrAg2OH2OHCH3HNMe3HOheat-NMe3-H2OCH3H28. Horner-Wadsworth-Rmmons反應（含穩(wěn)定碳負離子的磷酸酯在強堿作用下和醛，酮反應得到烯烴化合物）OOOMeOPOOMeH2COMeOMeLi

15、OOOP(OMe)3OOOHCOOEti-Pr(PhO)2PO+ PhCHONaH0oCi-PrCOOEtPhZ : E=99:1反應機理COOEtR2(R1O)2PO+ RCHOOEtOOCRR2H(R1O)2POerythroOEtOOCHR2R(R1O)2POthreoOEtOOCRR2(R1O)2POHOEtOOCHR2(R1O)2PORR2COOEtRCOOEtR2RZEHoffman 重排（酰胺在鹵素，強堿作用下降低一個碳原子得到伯胺）NFNH2OBr2KOHNNH2F反應機理RNH2ONa+-OBrRNHBrOOH-RNOBrRNCORNCOH2ORHNOHORNH2ROHRHN

16、OROHunsdiecker反應（干燥脂肪酸銀鹽和鹵素在無水溶劑中失去CO2生成鹵代烷烴和AgX）COOAgBr2 / heatBr+ CO2 + AgBr反應機理ROAgO+ Br2ROBrOROO+BrROOR+ CO2R+ROBrORBr +ROOKnoevenagel縮合（胺或其他堿的存在下，醛，酮與含活潑亞甲基的化合物縮合，生成,-不飽和酯）CHOOMeOMeEtOOCCOOEt+piperidineOMeOMeCOOEt反應機理ROOCCOORbaseROOCCOOROC COHCOORCOORH+C COHHCOORCOOR-CO2, OH-COOHC COHHCOOHCOOC

17、COHHCOOHCOOHH2ObaseONH+C NC NOH+EtOOCCOOEtNCOORCOORH-NHCOORCOORMannich-Eschenmoser反應（一分子甲醛，一分子仲胺和一分子含有 活潑氫的羰基化合物在銨鹽這樣的弱酸催化下縮合，在羰基化合物的 碳原子上引入一個氨甲基）CHOCHOOCOOHCOOH+ MeNH2+pH=5HCNMeCHCHCOOHCHCOOHOH2CH2CR H + HCHO+HNR CH2N-CO2HCNMeCHCH2CH2OH2CH2C反應機理NH2ClCH2O+HN+Cl+H2C OHHN+H2C OHNOHH-H2ON CH2PhCH3OPhCH

18、2OHNH2CPhCH2OH+PhON33. Michael加成（碳負離子與,-不飽和羰基化合物發(fā)生1，4-親核加成）OEtOCH2(COOEt)2NaOEtOEtOCOOEtEtOOC反應機理CH2(COOEt)2+CH(COOEt)2+ EtOH(EtOOC)2CH+CH3OCH3OCOOEtEtOOCEtOHCH3OCOOEtEtOOCHCH3OCOOEtEtOOCOEtMichael加成后分子內(nèi)發(fā)生Claisen縮合可得到DimedoneCH3OCOOEtEtOOCOEtOEtOOCCH2OOEt-EtOOCOO1) KOH2) H+OOOEtMitsunobu反應（醇的取代和構型轉化

19、）Ph3P+ROOCN NCOOR + ROH + H-NuPh3P O+RCOONHNHCOOR + R-NuOHDEAD, Ph3PPhH, PhCOOHOOCPhBnOC14H29OHDEAD, Ph3PphtalimideBnOC14H29PthN-BnOC14H29NH2N2H4反應機理Ph3P:EtOOCN NCOOEtPh3P OEtCOONHNHCOOEtEtOOCN NCOOEtPPh3H-NuEtOOCN NHCOOEtPPh3NuEtOOCN NHCOOEtPPh3NuOH+O PPh3NuO PPh3NuNu+Mukaiyama-Carreira醇醛反應(將一分子羰基化

20、合物預先制成更活潑的烯醇硅醚，在Lewis催化下與另一分子羰基化合物進行交叉Aldol反應）O1) LDA2) TMSClOTMSOTMSHOTiCl4OOTiClClClH2OO反應機理R3OR1TiCl4H2OR2R1OSi(CH3)3R3+OR5R4SiMe3R2OR4R5ClTiCl3-TMSClR5R3OCl3TiR1R2R4R4OHR5R2R1R3ONef反應（從硝基化合物制備醛，酮）NO2NaOHNOOH2SO4CHO反應機理HNRROO_+:BNRROO-+H+NRROHOH+H2O-H+RHORNOHOH-H2ON ORHORORR37. Peterson反應（-羰基負離子與

21、羰基化合物反應生成烯基化合物）Me3SiMgClPhCHOOPhTMSH2OPhHOTMSPhSiR3RCO3HOSiR3H3O+OHOHSiR3OHO反應機理OPhTMSH2OPhHOTMSH3O+ORTMSPhRLiRRbase(Na,K)OPhRTMSMe3SiPhROsyn elimPhRPhH2OTMSRH2OPhHOTMSRanti elimPhRPerkin反應（芳香醛與羧酸酐的反應）HO+ (RCH2CO)2ObaseArHCOOHR+RCH2COOH反應機理RH2COOH2CORbaseRHCOOH2CORArCHOArOHRHOOORH2OArHCOOHR+RCH2COOH

22、Pinacol反應（1，2-二醇用酸處理得到醛或酮）HOPhPhMeOHMeH2SO4MeOMePhPh反應機理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反應機理O2SOHNO2OH-SO2ONO2O2SONO2SNArOO2SNO2Me

23、isenheimer complexSommelet重排（苯甲基三甲基季銨鹽用鈉胺處理得到苯甲基三級胺）NMe3NaNH2CH3NMe2反應機理NaNH2CH2N(CH3)3H3CCHN(CH3)3H3CCH2N(CH3)2H3CCH2CH2N(CH3)2H3CHH3CCH3CH2N(CH3)2Stevens重排（強堿作用下季銨鹽中烴基從N原子遷移到相鄰C負離子的反應，锍鹽也可發(fā)生此反應）H3CNCH3RRH2CX-NaOEtH3CNCH3RRHCX-RRNCH3CH3HNMe2PhNaOEtNMe2PhNMe2PhSCH3PhOCH2CCH2PhNaOEtSCH3PhOCHCCH2PhPhO

24、SCH3Ph R為乙酰基，苯甲?；交任娮踊?；遷移基團R為烯丙基，芐基，取代苯甲基等。遷移基團上有吸電子基時反應速度加快。在Stevens重排中，遷移基團的構型保持不變。NPhOCH2CNaOEtMeMeCH3PhHNPhOCHCMeMeCH3PhHPhONMe2HPhMeStork烯胺烴基化和?；ㄈ┗蛲?jīng)過烯胺或亞胺的烴基化和酰基化反應）O+NOHTsOHNOCl(CH2)8OEt3NO(CH2)8ONC6H11EtMgBrNC6H11MgBrBrH3O+CHONNOMe1) LDA, 0oC2) Eu, -95oCNNOMeEtO3EtO反應機理OH+OHNHHONH+H2ON-H2OHN-H+NNRXNRXRNXHONROR+