反應(yīng)機(jī)理（課堂PPT）

1、.1一些重要的有機(jī)反應(yīng)機(jī)理一些重要的有機(jī)反應(yīng)機(jī)理1Arndt-Eistert反應(yīng)（重氮甲烷與酰氯作用形成 -重氮酮，在Ag離子催化下?；枷?重排得到烯酮。烯酮水解得到多一個(gè)碳的羧酸）RCOOHRCOClRCOCHN2RCH2COOHSOCl2CH2N2Ag2OwaterRCOCHN2ROH/Ag2ORCH2COORNH3/Ag2ORCH2CONH2.2反應(yīng)機(jī)理CH2N2RClOH2C N N+ROCH2N NROCHN N-重氮酮 Ag2OROCHN NROCHRCHC O碳烯 烯酮RCH2COOHRCH2COORRCH2CONH2RCHC OROHH2ONH3.32Arbuzov反應(yīng)（亞磷

2、酸酯在鹵代烷烴作用下異構(gòu)重排，生成烷基磷酸酯） (EtO)3P+CH3IrefluxEtOPOEtOCH3or(EtO)3P+BrOEtOrefluxEtOPOEtOOEtO反應(yīng)機(jī)理 OPEtOEtOEtRXOPEtOEtOEtRX-EtXEtOPROEtO.43Backman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(yīng)機(jī)理NRROHH+NRROH2-H2ONRRR C N RH2ONROH2R-H+NROHRHNROR.5 4Baeyer-Villiger氧化（醛或酮被過氧化物氧化得到酯或內(nèi)酯）反應(yīng)機(jī)

3、理RRORCO3HROORRRORCO3HROORRROHOOOROHRRH+B-+HORO烷基轉(zhuǎn)移順序：叔烷基仲烷基苯基正烷基甲基.65. Bamford-Stevens反應(yīng)（醛，酮的對甲苯磺酰肼衍生物在堿催化下生成烯烴）反應(yīng)機(jī)理R2HCR1NTsHNRRR1RLiR2HCR1NTsHN2RLiCR1N N TsRR-Ts-C CR1N NRRRRR1LiH2ORRR1H.76Benzidine（聯(lián)苯胺）重排 （氫化偶氮苯與強(qiáng)酸共熱，重排為聯(lián)苯胺）HNHNHClheatNH2H2N反應(yīng)機(jī)理HNHNHClheatNH2H2NH2NNH2HHNH2H2N-2H+.8Benzilic acid（二

4、苯羥乙酸）重排（鄰二酮化合物在強(qiáng)堿作用下生成二苯羥乙酸鹽）PhPhOOKOHPhPhCOOKHO反應(yīng)機(jī)理PhPhOOOH-PhPhCOOKHOHOOPhOPhHOOPhPhOH+.9Benzoin（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(shí)間加熱，發(fā)生雙分子縮合得到-羥基酮 ）PhHO2-CN, heatH2O, EtOHPhOPhOHH反應(yīng)機(jī)理PhHOPhOPhOHHCN+HPhCNOPh CCNOHPh COCNHOHPhPhOCNOHPhHPhOCNOHPhH-CN.10Birch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）

5、GNa, NH3 (liquid)EtOHGG= COO-, COOR, COR, CONR2, CN, Ar, SiR3 etc.Na, NH3 (liquid)EtOHGG=R, NR2, OR etc.反應(yīng)機(jī)理Na + NH3Na+ e-NH3氨溶劑化的電子很活潑R +e-RRHH=RHH-RHHHHRee-EtOHEtOHEtOH.11Bouveault-Blanc反應(yīng)（酯在鈉-醇體系中先還原成醛，再進(jìn)一步還原為伯醇）RCOORNaEtOHRCH2OH反應(yīng)機(jī)理RCH2OHRORONaROROEtOHROROHNaROROHEtOHRHOORHRCHONaRHOEtOHRHOHNaRHO

6、HEtOHEtOHEtO.12Brown硼氫化反應(yīng)（烯烴或炔烴與硼烷加成所生成的有機(jī)硼烷堿性氧化得到醇或醛地反應(yīng)）RROH1) R2BH2) H2O2, NaOH反應(yīng)機(jī)理RROHHBRRRHBRRanti-Malkovnicovsyn-additionRHBRRO OHRHBOOHRRROBRR-OOHROBOROR-OH+ B(OH)3.13Carroll 重排（堿催化下的烯丙基醇和-酮酯轉(zhuǎn)化為-酮羰基烯烴）OHR1R2OOOR1+baseR1R1O+ R2OH + CO2OHR1R2OOOR1baseR1R1OOR1R1OR1R1OR2OOOR1R1OObaseOOOR1R1anion p

7、romotedClaisen reactionOOOR1R1R1R1O+ CO2H+反應(yīng)機(jī)理.1413. Chugaev 反應(yīng)（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(yīng)機(jī)理ROH + CS2 + NaOHROSSNaMeIROSS+ NaICHC O CSSRCCHS COSRheatRSSHOCOS + RSH+.1514. Claisen 縮合（含-H的酯在堿作用下得到 酮酯）OEtOOEtO+baseOOEtO+ EtOH反應(yīng)機(jī)理CH2OEtOOEtOOOEtO+ EtOHH

8、H2COEtOH2COEtOOOEtOOEt-EtO-EtO.16Claisen重排（酚或烯醇的烯丙醚加熱至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(yīng)機(jī)理OOHOHheatheatOH3CCH3CH3H2COH3CH3CCH3OHH3CCH3OH.17Cope重排（1，5-二烯烴在加熱下3，3 遷移）300oCHOOheat反應(yīng)機(jī)理PhPhPhPhPhPh.18Cope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(yīng)機(jī)

9、理.1918. Corey-Chaykousky反應(yīng)（硫葉立德與親電物種如羰基，烯烴，亞胺，或硫碳基生成相應(yīng)環(huán)化物）反應(yīng)機(jī)理SCH2H3CH3CO(1) DMSYH3CSCH3CH2(2)RR1X(1) or (2)XRR1X= O, CH2, NR2, S, CHCOR3,CHCO2R3, CHCONR2, CHCNH3CSCH2OH3CRR1OH3CSOROH3CR1H3CSCH3OOR1R+.20Curtius重排（?；B氮化合物受熱脫氮重排得到異氰酸酯，進(jìn)一步水解，醇解和胺解生成胺，氨基甲酸酯和取代脲）NCH3PhCOOHH3CCOOH3CCOO1)PN3OPhOPhO, 80oC2)

10、 MeOHNCH3PhNH2H3CCOOH3CCOOPhCOOHH3CCH2CH31) SOCl2, Py2) NaN3, xylenePhNH2H3CCH2CH3.21反應(yīng)機(jī)理RClORNHOROONH2OEtONaN3HNO2NaN3RN N NORNCO+ N2RNCO+ H2ORNOHOHRNH2+ ROHRNOROH.2220. Darzens反應(yīng)（醛酮在堿作用下與 鹵代酸酯反應(yīng)生成，-環(huán)氧酯） OOEtClO+baseOH3CPhCOOEt反應(yīng)機(jī)理OEtClObaseORRCOOEtOEtClOOEtClORRO+RORCOOEtCl-Cl-.23應(yīng)用：在羰基碳原子上增長一個(gè)碳的醛

11、ORRCOOEtH+ORRCOOHH-CO2-H+RRHOHRCHOR.24Dieckmann縮合（含-氫的酯縮合生成五元，六元環(huán)化合物）EtOOCCOOEtNa or NaOEtOCOOEtEtOOCCOOEtNa or NaOEtOCOOEtCOOEtOEtOCOOEtEtOO+2EtO-COOEtOEtOCOOEtEtOOCOOEtCOOEtOO.25反應(yīng)機(jī)理COOEtCOOEtbaseCOOEtOEtOOOHHCOOEt-EtO-OHEtOOC-H+OCOOEtH+OHHOOC-CO2O.2622. Diels-Alder反應(yīng)（共軛二烯與親二烯體發(fā)生環(huán)加成得到六元環(huán)，反應(yīng)具有立體專一性

12、）反應(yīng)機(jī)理+TsMeOOCCOOMe+COOMeHHMeOOCCOOMeCOOMeCOOMeHHCOOMe.27Enamine（烯胺）反應(yīng)（二級(jí)胺與具有-H的醛，酮發(fā)生反應(yīng)）CHCONHRR+CHCOHNRRN RR反應(yīng)機(jī)理OH3C+NHNH3CBrNH3CH3O+OH3C.28Eschweiler-Clark反應(yīng)（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.29反應(yīng)機(jī)理RNH2OHH+RNHOHRNHCOOHRNHCH2RNHCHOOHRNHCH3

13、RNHCH3OHH+RNOHCH3H+RNCH3HCOOHRNCH3CH3+ CO2 + H+ orNH2HCHOHCOOHNCH2NH2ONOH.3025. Favorskii重排（ -鹵代（Cl or Br）酮在強(qiáng)堿（NaOH, NaOEt or NaNH2）作用下重排得到羧酸，酯或酰胺的反應(yīng)）OClCOOCH3NaOMe反應(yīng)機(jī)理RRXORO-RRXOHRHROHRHRO-ORHHOORRRRCOORRorRCOORR.31Hantzsch吡啶反應(yīng)（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 + NH3NHEtOOCCOOEtH3CCH3NEtO

14、OCCOOEtH3CCH31) NaOH, H2O2) CaO, heatNH3CCH3.32反應(yīng)機(jī)理EtOOCNH2H3CCH3ORCOOEtNH2RCOOEtEtOOCHH3CCH3ONH2H3COCH3COOEtREtOOCNHOHCH3COOHHEtOOCH3CRNHEtOOCCOOEtH3CCH3RNEtOOCCOOEtH3CCH3R.33Hofmann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(yīng)機(jī)理HCH3HNMe3BrAg2OH2OHCH3HNMe

15、3HOheat-NMe3-H2OCH3H.3428. Horner-Wadsworth-Rmmons反應(yīng)（含穩(wěn)定碳負(fù)離子的磷酸酯在強(qiáng)堿作用下和醛，酮反應(yīng)得到烯烴化合物）OOOMeOPOOMeH2COMeOMeLiOOOP(OMe)3OOOHCOOEti-Pr(PhO)2PO+ PhCHONaH0oCi-PrCOOEtPhZ : E=99:1.35反應(yīng)機(jī)理COOEtR2(R1O)2PO+ RCHOOEtOOCRR2H(R1O)2POerythroOEtOOCHR2R(R1O)2POthreoOEtOOCRR2(R1O)2POHOEtOOCHR2(R1O)2PORR2COOEtRCOOEtR2RZ

16、E.36Hoffman 重排（酰胺在鹵素，強(qiáng)堿作用下降低一個(gè)碳原子得到伯胺）NFNH2OBr2KOHNNH2F反應(yīng)機(jī)理RNH2ONa+-OBrRNHBrOOH-RNOBrRNCORNCOH2ORHNOHORNH2ROHRHNORO.37Hunsdiecker反應(yīng)（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(yīng)機(jī)理ROAgO+ Br2ROBrOROO+BrROOR+ CO2R+ROBrORBr +ROO.38Knoevenagel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）CHOOM

17、eOMeEtOOCCOOEt+piperidineOMeOMeCOOEt.39反應(yīng)機(jī)理ROOCCOORbaseROOCCOOROC COHCOORCOORH+C COHHCOORCOOR-CO2, OH-COOHC COHHCOOHCOOC COHHCOOHCOOHH2ObaseONH+C NC NOH+EtOOCCOOEtNCOORCOORH-NHCOORCOOR.40Mannich-Eschenmoser反應(yīng)（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(gè)氨甲基）CHOCHOOCOOHCOOH+ MeNH2+pH=5HCN

18、MeCHCHCOOHCHCOOHOH2CH2CR H + HCHO+HNR CH2N-CO2HCNMeCHCH2CH2OH2CH2C.41反應(yīng)機(jī)理NH2ClCH2O+HN+Cl+H2C OHHN+H2C OHNOHH-H2ON CH2PhCH3OPhCH2OHNH2CPhCH2OH+PhON.4233. Michael加成（碳負(fù)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(yīng)機(jī)理CH2(COOEt)2+CH(COOEt)2+ EtOH(EtOOC)2CH+CH3OCH3OCOOEtEtOOCEtOHCH3OCOOEtEtO

19、OCHCH3OCOOEtEtOOCOEt.43Michael加成后分子內(nèi)發(fā)生Claisen縮合可得到DimedoneCH3OCOOEtEtOOCOEtOEtOOCCH2OOEt-EtOOCOO1) KOH2) H+OOOEt.44Mitsunobu反應(yīng)（醇的取代和構(gòu)型轉(zhuǎn)化）Ph3P+ROOCN NCOOR + ROH + H-NuPh3P O+RCOONHNHCOOR + R-NuOHDEAD, Ph3PPhH, PhCOOHOOCPhBnOC14H29OHDEAD, Ph3PphtalimideBnOC14H29PthN-BnOC14H29NH2N2H4.45反應(yīng)機(jī)理Ph3P:EtOOCN

20、NCOOEtPh3P OEtCOONHNHCOOEtEtOOCN NCOOEtPPh3H-NuEtOOCN NHCOOEtPPh3NuEtOOCN NHCOOEtPPh3NuOH+O PPh3NuO PPh3NuNu+.46Mukaiyama-Carreira醇醛反應(yīng)(將一分子羰基化合物預(yù)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(jìn)行交叉Aldol反應(yīng)）O1) LDA2) TMSClOTMSOTMSHOTiCl4OOTiClClClH2OO反應(yīng)機(jī)理R3OR1TiCl4H2OR2R1OSi(CH3)3R3+OR5R4SiMe3R2OR4R5ClTiCl3-TMSClR5R3O

21、Cl3TiR1R2R4R4OHR5R2R1R3O.47Nef反應(yīng)（從硝基化合物制備醛，酮）NO2NaOHNOOH2SO4CHO反應(yīng)機(jī)理HNRROO_+:BNRROO-+H+NRROHOH+H2O-H+RHORNOHOH-H2ON ORHORORR.4837. Peterson反應(yīng)（-羰基負(fù)離子與羰基化合物反應(yīng)生成烯基化合物）Me3SiMgClPhCHOOPhTMSH2OPhHOTMSPhSiR3RCO3HOSiR3H3O+OHOHSiR3OHO反應(yīng)機(jī)理OPhTMSH2OPhHOTMSH3O+ORTMSPhRLiRRbase(Na,K)OPhRTMSMe3SiPhROsyn elimPhRPhH

22、2OTMSRH2OPhHOTMSRanti elimPhR.49Perkin反應(yīng)（芳香醛與羧酸酐的反應(yīng)）HO+ (RCH2CO)2ObaseArHCOOHR+RCH2COOH反應(yīng)機(jī)理RH2COOH2CORbaseRHCOOH2CORArCHOArOHRHOOORH2OArHCOOHR+RCH2COOH.50Pinacol反應(yīng)（1，2-二醇用酸處理得到醛或酮）HOPhPhMeOHMeH2SO4MeOMePhPh反應(yīng)機(jī)理OR1R3R2R4BF3R3OR1R2R4R2R1OHR3OHR4H+R2R1OHR3OH2R4R2R1OHR3R4R2OHR1R3R4-H+R2OR1R3R4.51Smiles重

23、排NO2YCCZNO2ZCCYY=S, SO, SO2, O, COO etc.Z=OH, NH2, NHR, CONH2, CONHR, SH, and CH3s conjugate baseO2SOHNO2OH-SO2ONO2反應(yīng)機(jī)理O2SOHNO2OH-SO2ONO2O2SONO2SNArOO2SNO2Meisenheimer complex.52Sommelet重排（苯甲基三甲基季銨鹽用鈉胺處理得到苯甲基三級(jí)胺）NMe3NaNH2CH3NMe2反應(yīng)機(jī)理NaNH2CH2N(CH3)3H3CCHN(CH3)3H3CCH2N(CH3)2H3CCH2CH2N(CH3)2H3CHH3CCH3CH

24、2N(CH3)2.53Stevens重排（強(qiáng)堿作用下季銨鹽中烴基從N原子遷移到相鄰C負(fù)離子的反應(yīng)，锍鹽也可發(fā)生此反應(yīng)）H3CNCH3RRH2CX-NaOEtH3CNCH3RRHCX-RRNCH3CH3HNMe2PhNaOEtNMe2PhNMe2PhSCH3PhOCH2CCH2PhNaOEtSCH3PhOCHCCH2PhPhOSCH3Ph.54 R為乙?；?，苯甲?；?，苯基等吸電子基；遷移基團(tuán)R為烯丙基，芐基，取代苯甲基等。遷移基團(tuán)上有吸電子基時(shí)反應(yīng)速度加快。在Stevens重排中，遷移基團(tuán)的構(gòu)型保持不變。NPhOCH2CNaOEtMeMeCH3PhHNPhOCHCMeMeCH3PhHPhONMe2HPhMe.55Stork烯胺烴基化和?；ㄈ┗蛲?jīng)過烯胺或亞胺的烴基化和?；磻?yīng)）O+NOHTsOHNOCl(CH2)8OEt3NO(CH2)8ONC6H11EtMgBrNC6H11MgBrBrH3O+CHONNOMe1) LDA, 0oC2) Eu, -95oCNNOMeEtO3EtO.56反應(yīng)機(jī)理OH+OHNHHONH+H2ON-H2OHN-H+NNRXNRXRNXHONROR+N