1、 T. S.ABCCAB = k r ABA + BA + BT. S.K =T. S. G= - RTlnK速度= KTh T. S. = KABK = e- G /RT速度= KThe- G /RT A+B反應物 D產物 G雙步 反 應G G1 G2 C中間體 A+B反應物 C產物過渡態 G單 步 反 應G G1ab GH GDRHRD過渡態一級動力學同位素效應氕取代和氘取代的零點振動能(CH3)2CCOC(CH3)2 + OH-H*H*(CH3)2CCOC(CH3)2H*H*OH-(CH3)2CCO-C(CH3)2H*kH/kD = 6.1過渡態RCOOR + H2O18OH-RCOO1

2、8H + ROHC+1234567XXHO+( I )( II )( III )( IV )Cl( a )Cl( b )TsOHHOTsOAcHHOAcHOAc+保持構型構型反轉XXX( V )( VI )( VII )k相對:15 1022.5 106CH2NH2 + NaNO2NH2 + NaNO2CH2OHOHOH+48%47-48%4-5%CH3CH214CH2NH2HNO2CH3CH14CH3OHCH3CH2CH2OH+1.9 2.2 95.9CH:BC:- + BH+R3R2R1:R1R2R3:R3R2R1:SP3雜化SP2雜化SP3雜化Ph-CH2P+PhPhPhCH2PPhPh

3、O:O(C6H5)3COOC(C6H5)3“ 六苯乙烷”2(C6H5)3C.2(C6H5)3C.+CPhPhPh3CHONaCONaH2SO4K2S2O8C HCH 單線態碳烯三線態碳烯Cl2CCO2-ClCO2Cl2CClCl2C:Cl-+ ;+COAr2CAr2COC C2H5COCN2HC2H5COC:HN2OO+ OOHHOHPhPhOHOHHOHPh2C=NNH2, PhI(OAc)2, CH2Cl2, -10C6H5C6H5C6H5C HO:C HC6H5+O HCH3CHCH3CH2I2,Zn CuHCH3CH2HCH3CCC %77HHCH3CH3%23CH3CH3HH.CH3

4、HCCH3HCH2CCCH2HCH3CHCH3.CCH2HCH3CHCH3.CH3HCCH3HCH2C:CH2( )HCH3CCH+CH3CH3+HCCCH3H):CH2( .CH3ONa,(2)(1) H2NNHTsO CH3CH3C CH.(CH3)2CCHCCH3CHCH350%9%+ R COOHR COCHN2-N2R COCHR COCHN2Ag2OH2ORCH C ORCH2COOHH2ORCH2COOH(1) SOCl2(2) CH2N2CH:. NNspsp單線態氮賓三線態氮賓.+E tOCON32 54nmE tO CONN2P hN3P hNN2. ArSO2O-+BH+

5、RNBRNHOSO2Ar. RCONOCNROCNHRC O2H2OOH. .+RNH2 NN H2NN.P b (C H3C OO )4 CH2CH2CH2CH3NO22(EtO)3PCH2CH2CH2CH3N3H2CNCH2CHHCH32(EtO)3PONCH3HRCONR3CHRCNHCR3O.+ H3C CHH2CCH2CHNHH 插入H3C CHH2CCH2HCNHH50%H2OH3C CHH2CCH2HCOHNHH3C20% 插入EtOCONEtOCON3EtOCONMeEtMeEtMeEtNEtO2CMeEtNCO2EtMeNEtCO2EtMeEtNCO2Et單線態三線態+PhN

6、3ArNPhNArN3OMePhNNArPhNNPhArNNArAr =ClCH3CH3NH2CH3NH2CH3NH2-+ PhCl + NH2NaPhNH2 + Cl + NaCH3ClCH3CH3ClHCl- HCl- HCl- HClCH3CH3CH3CH3CH3NH2NH2NH2+ NH3+ NH3+ NH3+ NH3O+OHHHHSP2 ClHNH2-Cl-Cl-NH2-NH2NH3NH2消去加成 F-FLiFLiFBr慢快 NH2CO2HHNO2N2+CO2-CO2N2+ NNNNH2Pb(OAc)4NiO2, 20 C+2N2 IIHgIIClIHgIOOOhv 或800700600hvhv或 ，Zn, 500600NH2NH2NH2NH2ZZZZZNH2-H+H+NH2-主反應 IIII2I-+ +溶劑質子性溶劑非質子性溶劑極性非質子溶劑非極性非質子溶劑A + BBABA + BBABAA + BBABAA + BBAB