反应机理1

一些重要的有机反应机理1．Arndt-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）RCOOHRCOClRCOCHN2RCH2COOHSOCl2CH2N2Ag2OwaterRCOCHN2R'OH/Ag2ORCH2COOR'NH3/Ag2ORCH2CONH2反应机理CH2N2RClOH2CNN+ROCH2NNROCHNN-重氮酮Ag2OROCHNNROCHRCHCO碳烯烯酮RCH2COOHRCH2COOR'RCH2CONH2RCHCOR'OHH2ONH32．Arbuzov反应（亚磷酸酯在卤代烷烃作用下异构重排，生成烷基磷酸酯）(EtO)3P+CH3IrefluxEtOPOEtOCH3or(EtO)3P+BrOEtOrefluxEtOPOEtOOEtO反应机理OPEtOEtOEtRXOPEtOEtOEtRX-EtXEtOPROEtO3．Backman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NR'ROHH+NR'ROH2-H2ONR'RRCNR'H2ONROH2R'-H+NROHR'HNROR'4．Baeyer-Villiger氧化（醛或酮被过氧化物氧化得到酯或内酯）反应机理RR'OR''CO3HROOR'RR'OR''CO3HROOR'RR'OHOOOR''OHR'RH+B-+HOR''O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R2HCR1NTsHNRRR1RLiR2HCR1NTsHN2RLiCR1NNTsRR-Ts-CCR1NNRRRRR1LiH2ORRR1H6．Benzidine（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+7.Benzilicacid（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）PhPhOOKOHPhPhCOOKHO反应机理PhPhOOOH-PhPhCOOKHOHOOPhOPhHOOPhPhOH+8.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+HPhCNOPhCCNOHPhCOCNHOHPhPhOCNOHPhHPhOCNOHPhH-CN9.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)EtOHGG=COO-,COOR,COR,CONR2,CN,Ar,SiR3etc.Na,NH3(liquid)EtOHGG=R,NR2,ORetc.反应机理Na+NH3Na++[e]-NH3氨溶剂化的电子很活泼R+e-RRHH=RHH-RHHHHRee-EtOHEtOHEtOH10.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）RCOOR'NaEtOHRCH2OH反应机理RCH2OHROR'ONaROR'OEtOHROR'OHNaROR'OHEtOHRHOOR'HRCHONaRHOEtOHRHOHNaRHOHEtOHEtOHEtO11.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)R'2BH2)H2O2,NaOH反应机理RROHHBR'R'RHBR'R'anti-Malkovnicovsyn-additionRHBR'R'OOHRHBOOHR'R'ROBR'R'-OOHROBOR'OR'-OH+B(OH)312.Carroll重排（碱催化下的烯丙基醇和β-酮酯转化为γ-酮羰基烯烃）OHR1R2OOOR1+baseR1R1O+R2OH+CO2OHR1R2OOOR1baseR1R1OOR1R1OR1R1OR2OOOR1R1OObaseOOOR1R1anionpromotedClaisenreactionOOOR1R1R1R1O+CO2H+反应机理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)MeIorMe2SO4OSS250oC+反应机理ROH+CS2+NaOHROSSNaMeIROSS+NaICHCOCSSRCCHSCOSRheatRSSHOCOS+RSH+14.Claisen缩合（含α-H的酯在碱作用下得到β–酮酯）OEtOOEtO+baseOOEtO+EtOH反应机理CH2OEtOOEtOOOEtO+EtOHHH2COEtOH2COEtOOOEtOOEt-EtO-EtO15.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OOHOHheatheatOH3CCH3CH3H2COH3CH3CCH3OHH3CCH3OH16.Cope重排（1，5-二烯烃在加热下[3，3]σ迁移）300oCHOOheat反应机理PhPhPhPhPhPh17.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)2OHRδ-δ+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）反应机理SCH2H3CH3CO(1)DMSYH3CSCH3CH2(2)RR1X(1)or(2)XRR1X=O,CH2,NR2,S,CHCOR3,CHCO2R3,CHCONR2,CHCNH3CSCH2OH3CRR1OH3CSOROH3CR1H3CSCH3OOR1R+19.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,xylenePhNH2H3CCH2CH3反应机理RClORNHOROONH2OEtONaN3HNO2NaN3RNNNORNCO+N2RNCO+H2ORNOHOHRNH2+R'OHRNOR'OH20.Darzens反应（醛酮在碱作用下与α–卤代酸酯反应生成α，β-环氧酯）OOEtClO+baseOH3CPhCOOEt反应机理OEtClObaseORR'COOEtOEtClOOEtClORR'O+R'ORCOOEtCl-Cl-应用：在羰基碳原子上增长一个碳的醛ORR'COOEtH+ORR'COOHH-CO2-H+R'RHOHRCHOR'21.Dieckmann缩合（含α-氢的酯缩合生成五元，六元环化合物）EtOOCCOOEtNaorNaOEtOCOOEtEtOOCCOOEtNaorNaOEtOCOOEtCOOEtOEtOCOOEtEtOO+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+COOMeHHMeOOCCOOMeCOOMeCOOMeHHCOOMe23.Enamine（烯胺）反应（二级胺与具有α-H的醛，酮发生反应）CHCONHRR+CHCOHNRRNRR反应机理OH3C+NHNH3CBrNH3CH3O+OH3C24.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-ClPhPhOHN反应机理RNH2OHH+RNHOHRNHCOOHRNHCH2RNHCHOOHRNHCH3RNHCH3OHH+RNOHCH3H+RNCH3HCOOHRNCH3CH3+CO2+H+orNH2HCHOHCOOHNCH2NH2ONOH25.Favorskii重排（α-卤代（ClorBr）酮在强碱（NaOH,NaOEtorNaNH2）作用下重排得到羧酸，酯或酰胺的反应）OClCOOCH3NaOMe反应机理RR'XOR''O-RR'XOHRHR'OHRHR'O-OR''HHOOR''R'RR'COOR''RorRCOOR''R'26.Hantzsch吡啶反应（氨或胺与β-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EtOOCNH2H3CCH3ORCOOEtNH2RCOOEtEtOOCHH3CCH3ONH2H3COCH3COOEtREtOOCNHOHCH3COOHHEtOOCH3CRNHEtOOCCOOEtH3CCH3RNEtOOCCOOEtH3CCH3R27.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）OOOMeOPOOMeH2COMeOMeLiOOOP(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)2PORR2COOEtRCOOEtR2RZE29.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-RNOBrRNCORNCOH2ORHNOHORNH2R'OHRHNOR'O30.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+ROO31.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α,β-不饱和酯）CHOOMeOMeEtOOCCOOEt+piperidineOMeOMeCOOEt反应机理ROOCCOORbaseROOCCOOROCCOHCOORCOORH+CCOHHCOORCOOR-CO2,OH-COOHCCOHHCOOHCOOCCOHHCOOHCOOHH2ObaseONH+CNCNOH+EtOOCCOOEtNCOORCOORH-NHCOORCOOR32.Mannich-Eschenmoser反应（一分子甲醛，一分子仲胺和一分子含有α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α碳原子上引入一个氨甲基）CHOCHOOCOOHCOOH+MeNH2+pH=5HCNMeCHCHCOOHCHCOOHOH