官能团转换

1官能团转换利用有机物的化学反应实现官能团转换是制备有机化合物的基本方法。一、转换成碳－碳双键的方法1．醇的消除反应CHCOHCC+H2OH2SO4活性顺序：叔醇仲醇伯醇；反应遵循札依采夫规律。2．卤代烷的消除反应CHCXCC+HXNaOH/ROH活性顺序：叔卤代烷仲卤代烷伯卤代烷；反应遵循札依采夫规律。3．季铵碱的消除反应CHCNR3OHCC+NR3+H2O反应遵循霍夫曼规律（得到双键上取代最少的烯烃）。二、转换成碳－碳叁键的方法二卤代烷或卤代烯烃的消除反应CHHCXXCC+HXNaOR/ROHCHCX2三、转换成碳－卤键的方法1．烷烃的取代反应CHhvX2CX+HX活性顺序：叔碳H、烯丙式H、苄基H仲碳H伯碳H；Cl2Br2。反应条件：光照、高温、过氧化物。2．烯烃、炔烃的加成反应CHCXCCHXCXCXCCX2CCHXCCHHXXCCHXHXCCX2CCXXXXCCXXX23．芳烃的取代反应X2FeX3X4．醇的取代反应COHHX或PX3CX活性顺序：叔醇仲醇伯醇；HIHBrHCl。5．重氮盐的取代反应NNXCuXX：Cl、Br，I取代时用KI。3四、转换成羟基的反应1．卤代烷的水解反应NaOH/H2OCOHCX活性顺序：碘代烷溴代烷氯代烷2．格氏试剂与醛、酮的加成反应CO(1)RMgX(2)H2OCOHR由甲醛得到伯醇、由其它醛得到仲醇、由酮得到叔醇。3．羰基、酯基、羧基的还原反应COCOHHH2/NiLiAlH4或NaBH4由醛得到伯醇、由酮得到仲醇。CR'OORCH2OHR'H2/NiLiAlH4CH2OHR+CROOHLiAlH4CH2OHR4．烯烃与水的加成反应CHCOHCCH2O/H2SO4按马氏规则，烯烃在酸催化下加水得不到伯醇（除乙烯外）；端基烯可以通过硼氢化反应得到伯醇。45．环氧乙烷及取代的环氧乙烷的开环反应OH2O/H+或OH-RROHROH或OROH(1)RMgX/(2)H2O6．伯胺与亚硝酸的反应R(Ar)NH2NaNO2/HClR(Ar)OH五、转换成氧桥（醚键）的反应1．醇的脱水反应H2SO4RCH2OHRCH2OCH2R+H2O2．Willianmson缩合反应R(Ar)ONa+R'XR(Ar)OR'+NaX六、转换成羰基的反应1．醇的氧化反应COCHOH[O]仲醇常用KMnO4、K2Cr2O7、HNO3等氧化剂，伯醇用CrO3－吡啶氧化成醛。2．炔烃与水的加成反应CCH2OHgSO4/H2SO4CCH2O3．烯烃的臭氧化反应COCCH(1)O3(2)Zn/H2OCOH+54．芳环上的酰基化反应（Friedel－Crafts酰基化反应）RCOX或(RCO)2OAlCl3RO5．-羰基酸酯的分解反应RCOOR'OYH3O+RYO七、转换成羧基的反应1．伯醇和醛的氧化反应RCH2OH[O]RCOOHRCHO常用KMnO4、K2Cr2O7、HNO3等氧化剂。2．由卤代烷的转化RXNaCNRCNH3O+RCOOHMg/Et2ORMgX(1)CO2(2)H3O+RCOOH3．甲基酮的卤仿反应CO(Ar)RCH3NaClOCOOH(Ar)R4．烷基苯的氧化反应CHKMnO4COOH只有含-H的取代苯才能被氧化。65．羧酸衍生物的水解反应CRYOH2O/H+或OH-CROH+HOYY:X,OCOR,OR',NH2,NHR2,NR'26．烯烃（炔烃）的氧化反应COOHRCHCH+RR'KMnO4/H+COOHR'COOHRCC+RR'KMnO4/H+COOHR'八、转换成氨基的反应1．硝基苯的还原反应NO2[H]NH2常用Fe/HCl、Sn/HCl、SnCl2等还原剂。2．卤代烷的取代反应RXNH3RNH2、R2NH、R3N官能团化和官能团的转换7芳烃的官能团化：RCORAlkylationAcylationReductionCH2RNitrationNO2SulfonationSO3HHalogenationXChloromethylationCH2ClArN2Cl,OHAr8烯烃的官能团化：RCH2-CH=CH2ReductionRCH2CH2CH3CarbeneadditionRCH2HCCH2H2CRadicaladditionRCH2CH2CH2Brα-HreactionHalogenationOxidizationRCHBrCH=CH2H2C=CHCHO(R=H)OxidizationRCH3CHCH2O,RCH2HCCH2OHOH,RCH2CHO+HCHOElectrophilicadditionHX(X=Cl,Br,I,HSO4,OH,OCOCH3)RCH2CHCH3XVWRCH2CHCH2Wδ+Vδ-(AsX2,HOX)9炔烃的官能团化：R-CCHNucleophilicadditionR'OHRCCH2OR'R'COOHRCCH2OCOR'HCNRCCH2CNElectrophilicadditionX2RCHX=CHX,RCX2CHX2HXRCX=CH2,RCX2CH3H2OR-C=CH2OHorRCCH3O①B2H6②OHRCH2CHOReductionRCH2CH3D-AreactionR10呋喃的官能团化：OCH3COONO2OO2NHOCOCH3HONO2ArN2ClOAr+OAr①HgCl2/NaOAc,②X2OXC5H5NSO3OSO3H(CH3CO)2OOCOCH3①(CH3)2NCHO,POCl3②H2OOCHO11噻吩的官能团化：SCH3COONO2SNO2HCHO,HClSCH2ClSXSSO3H(CH3CO)2OSCOCH3I2/HgOSIH2SO4NBS12吡啶的官能团化：NNNNNNElectrophilicsubstitutionNucleophilicsubstitutionBr2BrNitrationBrominationSulfonationAminationAlkylationHydroxylationNO2SO3HNaNH2NH2OHPhLiNPh13羟基的转换：ReductionO-alkylationEliminationHalogensubstitutionCHCOHCHCXCHCHCHCOREsterificationCHCOCORArOHHalogensubstitutionArXO-alkylationArOREsterificationArOCOR14氨基的转换：ArNH2(RNH2)N-alkylationArNHR'N-alkylationArNR2',ArNR3'N-nitrosationNNOArR'NNH2ArR'ReductionN-acylationArNHCOR'SulfamationArNHSO2Ar'DiazotizationArN2CouplationAr-N=N-Ar'HydrolyzationArOHH-substitutionArHCyan-substitutionArCNHalogen-substitutionArXNaBF4ΔArFNaNO2ArNO2ArN2BF4ReductionArNHNH2,ArNH2(R)(R)(R)(R)(R)(R)(R)CF3CO3HArNO215硝基的转换：ArNO2Fe/HClorH2/NiArNH2Zn/NH4ClArNHOHZn/NaOH(H2O)ArNHNHArZn/NaOH(CH3OH)Ar-N=N-ArAs2O3/NaOHAr-N=N-ArOOxidizationArNO氰基的转换：RCNHydrolyzationRCONH2,RCOOHAlcoholyzationRCOOR'ReductionRCH2NH2①R'MgX/ether②H3O+RCOR'16醛和酮的转换：RCH2CH(R')OReductionH2/NiorLiAlH4RCH2CHH(R')OHZn-Hg/HClRCH2CH2H(R')Addition①R''MgX②H3ORCH2CH(R')OHR''HCNRCH2CH(R')OHCNH3ORCH2CH(R')OHCOOHNaHSO3RCH2CH(R')OHSO3NaR''OH/HRCH2CH(R')OHOR''R''OH/HRCH2CH(R')OR''OR''CondensationHCHO,R1R2NH/HClRCHCH(R')OCH2NR1R2HCXY,R1NH2RCH2CH(R')NHR1CHYXRCH2CH(R')CXYOHR-CH2-C-CH-C-HHOHRO(R')(R')R-CH2-C=C-C-HHRO(R')(R')CH2COOEtCH2COOEtRCH2CH(R')CCOOEtCH2COOEtR''CHCOOEt,RONaXRCH2CH(R')CR''COOEtO①XCH2COOEt/Zn②H3ORCH2CH(R')OHCH2COOEtPh3P=CR2'RCH2CH(R')CHCOOEtNH2-YRCH2CH(R')N-Y(Y:OH,NH2,NHPh,NHCONH2,etc.)17羧基的官能团转化：RCOOHReductionRCH2OHEsterificationRCOOR'ReductionRCH2OH+R'OH①R''MgX②H2OCRR'OHR''R''OHRCOOR''+R'OHR''COOHR''COOR'+RCOOHR''CH2COR'''/EtONaRCOCHCOR'''R''R''CH2COOR'''/EtONaRCOCHCOOR'''R''AmidationRCONH2NaOXRNH2LiAlH4RCH2NH2-H2ORCNRCOXNH3NH3HalogenationReductionRCH2OH,RCHOR'MgX/etherRCOR',CR'OHRR'ArH/LewisacidArCORR'OHRCOOR'Δ(RCO)2ORCOONaArH/LewisacidArCORNH3RCONH218卤素的官能团转化：R-CH2-CH-R'XKOH-C2H5OHR-CH=CH-R'LiAlH4RCH2CH2R'Mg/etherR-CH2-CH-R'MgXLi/N2R-CH2-CH-R'LiNaR-CH2-CHR'2OHCNR''ONHR1R2R''CCNaR''MgXNaSHNaSR''Na[CH(CO2Et)2]R-CH2-CH-R'OHR-CH2-CH-R'CNR-CH2-CH-R'OR''R-CH2-CH-R'NR1R2R-CH2-CH-R'CR-CH2-CH-R'R''R-CH2-CH-R'SHR-CH2-CH-R'SR''R-CH2-CH-R'CH(CO2Et)2CR''