第五章卤代烷(1)

1、(Alkyl halides) 本章目录本章目录CHCCl3ClClCF2CF2nRC lRB rRI,RFRCH2XCHXRRCXRRRCXRRXCXRRCRXRCRRCRXXCH3CH2CH2CH2Br正正溴溴丁丁烷烷CH3CH2CHBrCH3仲仲溴溴丁丁烷烷CH3CBrCH3叔叔溴溴丁丁烷烷CH3正正丁丁基基溴溴仲仲丁丁基基溴溴叔叔丁丁基基溴溴CH3CHCH2BrCH3异异丁丁基基溴溴异异溴溴丁丁烷烷三三氯氯甲甲烷烷氯氯仿仿, , chloroformn-butyl bromidesec-butyl bromidetert-butyl bromideisobutyl bromideCHC

2、l3ClClCF2Cl2HCNOFClBrISP2.12.53.03.54.02.12.53.02.82.5CX CF3CCl3 ,（强强）吸吸电电子子基基团团(electron withdrawinggroup)CRC Cl CRCClClCl ( SNNucleophilic Substitution Reaction)CXCX+CXCX+Nu NuCHRWW: 吸吸电电子子基基（electron withdrawing group）有有弱弱酸酸性性B（碱碱）CRW+HB CHRCH X BCRCH +X+HB消消除除 H成成烯烯烃烃5-3 5-3 一卤代烷的反应一卤代烷的反应CXCH-+

3、NuRX+XRNu+NuRX+XRHNu+HOHORSHSROHRORRSHRSRR醇醇醚醚硫硫醇醇硫硫醚醚OCOROCORR酯酯NuR+XRNuCNCCR炔炔基基负负离离子子CNRCCRR腈腈高高级级炔炔丙丙二二酸酸酯酯负负离离子子CH(CO2Et)2R烷烷基基丙丙二二酸酸酯酯IIRCH(CO2Et)2NuR+XRNu碘碘代代烷烷HOHHORHNH2HNHRHNR2NR3(水)(醇)(氨)(伯胺)(仲胺)(叔胺)ROH醇醇ORR醚醚RNH2伯伯胺胺RNHR仲仲胺胺RNR2叔叔胺胺RNR3 X季季铵铵盐盐NuR+XRHNuNaOH or H2OOHRORRNaOR or HORNH2RNH3O

4、CORRRCOONaCCRRCCRNaCCRXMgorCH(CO2Et)2RNaCH(CO2Et)2RXCNRNaCNAgNO3 AgX动力学证据动力学证据反应速率反应速率立体化学证据立体化学证据对手性底物，对手性底物，产物的立体化学产物的立体化学重排重排现象现象反应类型反应类型I I RXNu构型翻转构型翻转无无双分子机理双分子机理bimolecular mechanismIIII RX消旋化消旋化有有单分子机理单分子机理unimolecular mechanismNuRX+XR+NuNuXRNuRXNuRX+过过渡渡态态NuRX+NuRXNuXR+势势能能反反应应进进程程 C6H13H3C

5、BrH+NaOHC6H13CH3HOH+NaBr构构型型发发生生转转换换与与 SN2 机机理理吻吻合合C6H13H3CBrHOHC6H13CCH3BrHHO C6H13CH3HOH+Br仲仲卤卤代代烷烷XRRNuNuR势势能能反反应应进进程程XRXRRX+NuRX+慢慢快快 R1R2XR3Nu+R1R2NuR3R1R2NuR3+叔叔卤卤代代烷烷与与 SN1 机机理理吻吻合合R1R2XR3R1R2R3 XNuR1CR2NuR3()SN2SN2: = - 34.6 = +9.9（SN1）(CH3)3Br + OH- - C+ Br- - R1R2R3H2OH2OH2OSN1+重排CH3 C- CH

6、 CH3CH3H3C+H2OCH3- C- CH- CH3CH3H3COHCH3-C-CH-CH3CH3BrH3CCH3-C-CH-CH3CH3H3C-H+ SN1BrC CCH3HO- -=OBr- -分子内分子内SN2OH- -C CCH3HO=OOHC CCH3HO- -=O：-COO- -, -O- -, -OH, -OR, -NR2, -X。R2CHR3C1o2o3oCH3sp2 杂杂化化平平面面型型RCH2(CH3)3CF+(CH3)3CSbF6可可通通过过核核磁磁共共振振观观察察到到SbF5超超酸酸RHRH+RR+e 键键离离解解能能 电电离离能能RHRH+e 3o2o1oCH3

7、,PhCH2CH2=CHCH2 H (KJ/mol)13161130100010719701040(CH3)3C+ (CH3)2C+H CH3C+H2 +CH3CHRCH2RRCCH p - 超共轭超共轭 - p 超共轭超共轭C CHHHRR+CHRORCHRORCHXRCHXRppppCHCHHH2CH pCHHH p（诱导）吸（诱导）吸CCF3CCCl3CCOCNO2CCH2HHH3CH2CCCH2H3CH2CHHHCCH2HH3CH2C HCCH2CH3HH3CH2CCCH2H3CH2CCH3H HCCHCH3CH3CH3H3C CH3CCHCH3CH3CH3H3CCH3CH2Br+NaOHCH3CH2OHNaBr+CH3CH2BrOHCH3CH2OH+BrCH3CBrCH3CH3+H2O乙乙醇醇CH3COHCH3CH3HBr+CH3CBrCH3CH3CH3CCH3CH3H2OBrCH3COHCH3CH3CH3COHCH3CH3+HBrHBrCCH2BrCH3CH3H3CCCH2OC2H5CH3CH3H3CC2H5OHCCH2CH3CH3O