重排反应及酰化反应练习题和答案

第六章重排反应练习题一、完成从C到C的重排反应（1）CH2BrCH3H3CCH3AlBr3-AlBr4（2）NH2H3CONaNO2/HOAc（3）PhCOHPhCOHPhPhTsOHH2O-H+（4）H3CCOHH3CCOHPhPhH+-H2O（5）H3CCOHH3CCOHPhPhAc2O/ZnCl2或含痕量H2SO4的HOAc（6）PhHCOHCPhOHCH3HCl(g)25,3h（7）OHCOHPhPhH2SO4/Et2O（8）OHOH0.4mol/LSnCl4/CH2Cl2(PhO)2CHOEt（9）H+-H2OOHCH3CH3OH（10）H+-H2OCH3CH3OHOH（11）ClC(R)OHPhCHBrPhAgNO2/EtOH（12）HOCH2NH2HNO2（13）CCOOKOH/EtOH加热（14）OClNaOH（15）CH3CH3N2OMeOH(16)MeOON2hv-H2O(17)COOHSOCl2CH2N2AgO/H2O二、完成从碳原子到杂原子的重排反应(1)MeCHMe2NHOlewis酸(2)OHH3CNOHZnCl2(1:1),20min(3)n-BuCEtCHMeNOHH2SO4/醚(4)ClFClFCNH2Oaq.NaOH/NaOCl(5)NNCNH2NH2F3COBr2/KOH(6)CNH2OPhI(OAc)2/KOH/CH3OH(7)HCCONH2XHofmann重排R(8)CHCHCONH2Hofmann重排R(9)CONH2CH3OHC11H23NBS/CH3COOAg/DMF(10)NNCO2CH3ClONaN3/丙酮/H2OC6H6(11)ONHCON3加热(12)HOOCCH3CH3COOHNaN3/H2SO4/CHCl3r.t,25h(13)PhCH3OHN3/H2SO4(14)OCOOH+NH3H2SO4(15)ORCO2EtHN3(16)HCCH3OPhCO3H/CHCl3(17)O2NCOCH3CO3H/AcOH(18)NRR1PhOOH间氯过氧苯甲酸/CH2Cl2(19)NRCHOOMeOHH间氯过氧苯甲酸/CH2Cl2三、完成从杂原子到碳原子的重排反应（1）CHCH2RR1NMeMeCH2CNHR2OKOH/C6H6+DMSO(2)NPhOLDA/THF/-78℃(3)NCO2EtMeCH2PhBrNaOEt/EtOH(4)CH2CNCPhHCH3ONaNH2/C6H6H3C(5)RNMe2CH2SiMe3CsF/HMPA(6)NMeCH2SiMe3ICsF/DMF(7)PhNHSCH3CH3NaNH2/liq.NH3(8)NOMePhOPh2eq.LDA/THF(9)MeOONOMeLDA/THF(10)ONOMeMeOCH2OMeBuLi/THF(11)H2CCHH2CNCH3CH3NaH/THFCH[P(OEt)2]2O(12)SCH3XF/liq.NH3四、完成σ键迁移重排反应(1)OCH3CH3R加热(2)OOORR2R1OMe甲苯reflux(3)OCF3CH3Ph甲苯100℃,2h(4)O(PhP3)3RuCl2(5)HOOCH2PhOMeOMeLDA/THF/Me3SiCl(6)OCH2CHOCH3H3COCH2Δ(7)H3CCH3CH3OBCl3(8)NSOOOCH2CHCH2150℃(9)SNOCH2CHCH2Δ(10)NOOCO2EtNHArCH2C6H6reflux,24h(11)SCH2CH2重排(12)SMeSMeMeOCH2Ph[3.3]-σ3h,20℃(13)SSCH2CHCH2TMPA/N2170~180℃(14)NMeCH2CHCH2AlCl3140℃,8h(15)NMeCH2CHCH2BF3(Et2O)2(16)NCH3OPhLHMDS/THF(17)NH3CH3CBuOLDA/THF(18)PhPh150℃(19)[3.3]-σΔ(20)HOCope重排(21)HCCCH2ClCH2CH2HOHCope重排(22)OHCH3OHCH3190℃(23)PhNPhaza-Cope重排HCl/C6H6(24)NHNCCH2CH3PhAlCl3(25)NHNCH3NZnCl2(26)NHOH稀H2SO4(27)HNOONaOCl/NaOH(28)NCONHOHHCONH2(29)NHNHH(30)CH2N(CH2)3NaNH2/NH3I(31)H3CCONHPriOO1.KOH/甲苯,4h2.冰水(32)O+NH2OH.HClHCOOH/SiO2(33)OCH3N3TFAA(34)COCHN2C6H5COOAg/EtOH/Et3N(35)OMeO2NOMeCHN2OMeOMeOAgNO3/THF-H2O(36)OCl+CH3ONaΔEt2O(37)OOR3SiCClR3N(38)OC6H5C6H5HHBF3(39)RCHCHOHR1OH[Pd](40)OCOCH3OMehv/K2CO3/正己烷(41)OLiBr/HMPTC6H6(42)OHRCHR1400-500℃(43)CHOOTIPSOMe(MeO)2PCHN2Ot-BuCOK-78℃(44)CCl(C6H5)3PClClt-BuCOKH2CClS(45)hv(46)H3CCH3CH3CH3H2SO4(47)COHHRuCl3H(48)RNEt2chiralRh(I)H(49)OPd(PPh3)4(50)RHCCBrROAgBF4H2O(51)RH2CHCCCHOCH2LewisacidCH3(52)RHOOn-BuLi(53)ROCROcatPd(PPh)3dppe第六章重排反应答案1.从C到C的重排wanger-meerwein（1）H3CCH3CH2CH3Br（2）COOClPinacol（3）PhCOCPhPhPh（4）H3CCOCCH3PhPh（5）PhCOCCH3PhCH3（6）PhCOCPhHCH3（7）OPhPh（8）OCH3（9）CH3CH3O（10）CHCH3CH3OSemipinacol（11）ClCHPHPhO（12）O二苯基乙二酮-二苯基乙醇酸型重排：（13）COHCOO-Favorski：（14）COOHwolff:(15)CH3CH3COOMe(16)COOH(17)COOCl，COCHN2，CH2COOH2.从碳原子到杂原子的重排Beckmann:(1)NHMeCHMe2O(2)ONCH3(3)n-BuCEtHNHMeOHofmann:(4)ClFClFNH2（5）NNF3CNNOH（6）NHCO2CH3(7)RCHO(8)CHO(9)C11H23COOCH3Curtius:(10)NNCO2CH3N3O,NNCO2CH3NH2(11)ONHNCOSchmidt(12)HOOCCH3CH3NH2(13)CH3OHNPh(14)NHOCOOH(15)NHORCO2EtBaeyer-villiger:(16)HOCCH3O(17)O2NCOO(18)NRR1PhHOOO(19)NROMeOHHOCHO3.丛杂原子到碳原子的重排Stevens:（1）H2CCHCRR1HCNMe2CNHR2O(2)NPhH(3)NCO2EtMeCH2Ph(4)CHC(H3C)NOCPhHCH3Sommelet-hauser:(5)RMeNMe2(6)HMe(7)NH2PhCH2SMeWitting:(8)NOMePhPhOH(9)MeONOMeOH(10)ONMeMeOHOCH2MeH(11)H2CCHH2CC[P(OEt)2]2NMe2O(12)S4.σ键迁移重排：Claisen(1):OCH3CH3R(2)OOOHRR1R2OMe(3)OCF3CH3Ph(4)CH2CHOCH3(5)HOOCH2PhCO2H(6)OHH3COOCH3CH2CH(7)H3CCH3CH3OH(8)NSOOOCH2CH(9)SHNCH2CHO(10)NOOHCO2EtNHAr(11)CH2CH2CHCHSH2C（12）SMeSMeOCH2PhMe(13)SS(14)NHMeCH2CHCH2(15)NHMeCH2CHCH2(16)NHOPh(17)NHBuOH3CH3CCope:(18)PhPh(19)HH(20)O(21)OCH2Cl(22)OO(23)PhNMePh,MePhOFischer吲哚合成：(24)NHMePh(25)NHN《新编有机合成化学》〉黄宪主编(26)羟胺重排：，H2NOH(27)Hofmann重排,NHO(28)Lossen重排：NNH2(29)联苯重排：NH2NH2(30)Sommelet重排：CH3CH2N(CH3)2(31)Smiles重排：NHPriH3CCO(32)Beckmann重排：CNHO(33)Schmidt重排：CH3O(34)Arndt-Eistert-Wolf重排：CH2COOC2H5,(35)OMeO2NOMeOMeMeOCOOH(36)α-卤代酮的重排：COOCH3(37)烯丙酯的重排：CO2H(38)环氧化合物重排：(C6H5)2CHCHO(39)炔丙醇的重排：RR1OO(40)Fries重排：OHOMeCOCH3(41)环氧乙烷衍生物的重排：HCHO(42)不饱和醇的重排：HRO+H2CCHCH2R1(43)重氮烯的重排：OTIPSOMeCCH(44)α,α-二氯砜及α,α-二溴酮的脱卤化氢重排：CClClC(45)小环化合物的重排：(46)烷基苯的重排（Jacobsen反应）：H3CCH3CH3CH35.ComprehensiveorganicTransformationsSecondEditionIsomerization(1)H3CH2COComptRendC1257(1973)(2)RCHO2.Epoxides(3)HCCCCHCOJACS101162361979(4)RHCCROHOTL366519(1995)(5)RCH2C(Me)CHCHOCH2JACS1177379(1995)(6)ORJACS11712700（1995）第四章酰化反应练习题一、完成下列反应1、ClClO+AlCl32、NHHNOClOCl3、NHHNOClOOCl34、NHHNONaHCH3COCl5、NHHNOSO2Cl6、OOOAlCl37NHSCH3COOCCH3O8NH2COOH(CH3CO)2OCH39NNSH2NSHCH3COOCCH3O10NH2OHCH3COOCCH3O11NH2CH3COOH12NH2F3CClCOCl2CH3CN13NHNH2OOO14OCOCl+(CH3)2CHCH2CHCOOCH2OH15NH2CF3COCl2CH316COOHNO2HOCH2CH2N(C2H5)2xylene17CH3NH2CH3ClCH2COCl18H3CH2N+H3COClOEt3N,DMF19NHCH3CClOClCH2COClC6H1220F+ClClOAlCl321OHAC2O22OHOHO+H3COCH3OOH2SO423H3CONHNHSO3NaClCOCl24NHClClClCH2COCl25H3CCH3CH3COClAlCl326H3COCH3CH2COClAlCl327HOHOPOCl3,ClCH2COOH28H3CSClOCH3OHNOHO29、HCCHClClOAlCl330、NSNH2OOOOC2H5OHH31、SOOO32、OOOOH3PO433、1）NHNOTMSClNONNOOTMSClClO2）NHNOOClOO2N23）NHNOOCl3O3OCCl3O.33、COOHSOCl2AlCl334、OHCoCl2NaOHTolCH2NH2NaOH35、NHCOCl2TolBr2-HBrNH3C2H5OH36、COOHH2NNH2III(CH3CO)2O37、NNHOEt2NClO38ClClFAlCl3CH3COCl39OHOClAlCl340OO2NHCCHCOOHPCl541NH2COOHAc2O