第四章线性自由能关系2

1L.P.Hammett,JACS,1937,59,96,HammettKa=logKaoXCOOHH2OXCOOH3O(1)Ka=logKao(2)HammettHammett,(2)(3),(4)(5).:CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter20,0,AcOMeCONH2AcNHMeBrClFHOMeOCF3CNNO2Me3Np+0.31+0.47-0.300.0-0.14+0.26+0.24+0.15-0.38-0.27+0.53+0.70+0.81+0.96m+0.39+0.36-0.09+0.14-0.06+0.37+0.37+0.34+0.15+0.16+0.46+0.62+0.71+0.99Taft,R.W.Chem.Rev.1991,91,165.i)MesomericEffectorResonanceEffectii)InductiveEffect(FieldEffect):p-OMe=-0.27m-OMe=+0.16,m,mmp+pm.NO2pOMe:p0,m0(p,+C;m,-I)2.Hammettklgko=CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter30SN2HOCCl0,0,0,0,0,00,0=0lgkko=kkokkokkokkoHammettlog(k/kH)log(K/KH)Y,X,:1)Hammett2)3)0,,()4)1,5)01,,CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter46)0,,7),Diels-Alder8)logklogKvs,1)p-OMe0000)10)ArCPhHCl-ClArCPhHC2H5OHArCPhHOC2H5ArCOOC2H5OHArCOC2H5OOHArCOOHOC2H5=-5.0=+2.5CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter5NH2XPhCOClXNHHCOClPh-HXNHCOClPhClXNHCOPh=-2.69:=2.7Wittig,=2.7Ar3PCO2EtOHXAr3PXCO2EtOAr3PXCO2EtOEtO2CXHammett125=+0.47KH=3.6510-5p-NO2=-0.069Hammettlg(Kp-NO2/KH)=p-NO2=0.470.78=0.37Kp-NO2=8.4910-5lg(Km-Me/KH)=m-Me=0.47(-0.069)=-0.032Km-Me=3.3910-510000002=2.38,ko=210-4kmm-NO2=0.71Hammettlgkm/ko==0.712.38km/ko=49,km=9810-4mol-1·s-1,p()CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter6p-NO2p-CNp-CNp-NO2,ThroughConjugationp-NO2,-CO2-p-(Through-Conjugation)(+2.01),Hammettpp-OMep-Me,.,,H.C.Brown+CumylChloride=-4.45CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter7H.C.BrownandY.OkamotoJACS,80,4872(1958).,YukawaTsunoHammettYukawa-Tsunor,0~1r;r=0,Hammett,:=+3.52,=0.50,22=4.45,r=1rHammettAcetoxyBs=p-BrC6H4SO21.Hammett(Concaveuploads)CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter8(diastereoisomer)1HNMRp-OMep-NO2SN12.ArCO2R99.9%H2SO4AAC2+0.03=-3.25AAC2(Acid-Catalyzed,Acyl-OxygenCleavage,Bimolecular)CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter9AAC1Acid-CatalyzedAcyl-OxygenCleavage,Unimolecular=+2.0O-EtAAL1(Acid-CatalyzedAlkyl-OxygenCleavage,Unimolecular)CH3CH2CH3CH3CH2AAC1AAL13.HammettConcavedownwardsderivationsCyclodehydrationof2-phenyltriarylmethanols,H.Hartetal.,JACS1967,89,2342=2.673ZMeO3CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter10S-1.0~+4.4eusp3sp2SS=-4.9~-16.7euHammett1)HammettHammettXk1k2k20Xk10H.HartandE.A.Sedor,JACS,89,2342(1967)J.Hoffmannetal.Coll.Czech.Chem.Comm.35,1387(1970)2)HammettHammettCreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter111Hammett.21.pka3.98pka4.197-1N,N-90%=-3.30XN(CH3)2++CH3XN+(CH3)37-2pKa=10,m-NO2=+0.710,25C=2.11pKapKa=8.5CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter127-3Ar—ArCH2Cl+I-ArCH2ICl-ArNH2C6H5COClC6H5CONHArHClArCOClC6H5NH2ArCONHC6H5ArO-H2CCH2OArOCH2CH2O-1234++++HCl++ArSO2ClAlCl3ArSO2+AlCl4-C6H6ArSO2C6H5H+ArCHOHSCH2CHCOOHNH2SCHNHCHCH2COOHArH2O56+++++5.06.01.02.03.04.07-4XCH2N+H(CH3)2XCH2N(CH3)2+H2O9.03H8.83p-Cl8.67m-Cl8.14p-NO28.198.949.229.32pKam-NO2p-Fp-CH3p-CH3OXHammett=1.13X7-8=2.38k=2x10-4mol-1s-1,kk=9.77x10-3mol-1s-17-9=-1.31ArCH2ClH2OArCH2OHHCl++NO2CH2ClBrCH2ClkBr/kNO2kBr/kNO2=5.27-10HF+3.24+3.56+4.04ArCH2CH2FArCH2CHF2ArCH2CF3CreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter137-11-7.29-2.39+0.75=+2.451.2.3.4.N,N-1.=-7.29;2.=+2.45;3.=+0.75;4.=-2.39Hammett7-12NH2H3COOCH3pKpK=4.57,=+0.115,=+2.81pK=3.92Hammett50,Taft,=fF+rR,=0,TaftEs,(,)Taft,,X,,.,Taft:B:,2.48?–,Hammett:TaftTaftCreatePDFwithGO2PDFforfree,ifyouwishtoremovethisline,clickheretobuyVirtualPDFPrinter