大學本科有機化學鹵代烴

1、1n鹵代烷的類型和命名n鹵代烷的親核取代，取代產物的類型n親核取代反應的兩種機理SN1和SN2機理， 兩種機理在反應動力學和立體化學上的不同之處n正碳離子，正碳離子的穩(wěn)定性，正碳離子的重排2飽和鹵代烴CHCl3CHClF2Cl3C CH3F3C CHClBrC CClHHHC CFFFFClClOIIH2C CHNH2COOHIIHO不飽和鹵代烴芳香鹵代烴F-12Halothane不燃燒的麻醉劑特氟隆單體甲狀腺素3C HCClClClClClDDT4The Nobel Prize in Physiology or Medicine 1948for his discovery of the hi

2、gh efficiency of DDT as a contact poison against several arthropods5RX （ X = F, Cl, Br, I）RClRBrRI,RF6RCH2XCHXRRCXRRRCXRRXCXRRCRXRCRRCRXX7CH3CH2CH2CH2Br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異異丁丁基基溴溴異異溴溴丁丁烷烷三三氯氯甲甲烷烷氯氯仿仿, , chloroformn-butyl bromidesec-b

3、utyl bromidetert-butyl bromideisobutyl bromideCHCl38選取含鹵素的最長碳鏈為主鏈CH3CH2CHCH2CH3CH2Br2 乙乙基基 1 溴溴丁丁烷烷CH2CH2CCH2CH3CH3HBr(S) 3 甲甲基基 1 溴溴戊戊烷烷CH2ClCl反反 1 氯氯甲甲基基 4 氯氯環(huán)環(huán)己己烷烷CH3ClCHCH3CH2CH3(R) 2,3 二二甲甲基基 3 氯氯戊戊烷烷CH3910HCNOFClBrISP2.12.53.03.54.02.12.53.02.82.5CX CF3CCl3 ,（強強）吸吸電電子子基基團團(electron withdrawing

4、group)CRC Cl CRCClClCl 11 *12( SNNucleophilic Substitution Reaction)CXCX+Nu NuCXCX+13CHRWW: 吸吸電電子子基基（electron withdrawing group）有有弱弱酸酸性性B（堿堿）CRW+HB CHRCH X BCRCH +X+HB消消除除 H成成烯烯烴烴Elimination Reaction)14 ）NuRX+XRNu+NuRX+XRHNu+H底物 (substrate)親核試劑： 至少含有一對未共用電子對15OHORSHSROHRORRSHRSRR醇醇醚醚硫硫醇醇硫硫醚醚OCOROCOR

5、R酯酯NuR+XRNu16CNCC R炔炔基基負負離離子子CNRCC RR腈腈高高級級炔炔丙丙二二酸酸酯酯負負離離子子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17HOHHORHNH2HNHRHNR2NR3(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季季銨銨鹽鹽NuR+XRHNuXH+18RX+ AgNO3C2H5OHRONO2+AgX 3。RX 2。RX1。RX( X 原子相同 )1920 RX為重要有機中間體（intermediates）RXORRSHRS

6、RROCORRCNRCC RRCH(CO2Et)2RIRNaOH or H2ONaOR or HORNaSH or NaSRNHR2(H)CCRNaCCRXMgorNaCH(CO2Et)2NaCNNaIRCOONa酯酯腈腈高高級級炔炔烷烷基基丙丙二二酸酸酯酯醇醇醚醚伯伯胺胺仲仲胺胺叔叔胺胺硫硫醇醇( (硫硫醚醚) )OHRNH2RNHRRNR2R碘碘代代物物21NuXRNuRXNuRX+過過渡渡態(tài)態(tài)NuRX+NuRXNuXR+勢勢能能反反應應進進程程 22XRRNuNuR勢勢能能反反應應進進程程XRXRRX+NuRX+慢慢快快 23動力學證據動力學證據反應速率反應速率立體化學證據立體化學證據對

7、手性底物，對手性底物，產物的立體化學產物的立體化學重排重排現象現象反應類型反應類型I I RXNu構型翻轉構型翻轉無無雙分子機理雙分子機理bimolecular mechanismIIII RX消旋化消旋化有有單分子機理單分子機理unimolecular mechanismNuRX+XR+Nu24C6H13H3CBrH+NaOHC6H13CH3HOH+NaBr構構型型發(fā)發(fā)生生轉轉換換與與 SN2 機機理理吻吻合合C6H13H3CBrHOHC6H13CCH3BrHHO C6H13CH3HOH+Br仲仲鹵鹵代代烷烷25R1R2XR3Nu+R1R2NuR3R1R2NuR3+叔叔鹵鹵代代烷烷與與 SN

8、1 機機理理吻吻合合R1R2XR3R1R2R3 XNuR1CR2NuR3()26鹵代烷親核取代的兩種機理： SN2 和 SN1 機理27RX R+X- R+ X- R+ + X-內返離子對外返離子外返緊密離子對溶劑分離子對游離離子實例分析CHCH3CHCH3Cl*CHCH3+OH40%水-丙酮28(CH3)3CF+(CH3)3CSbF6可可通通過過核核磁磁共共振振觀觀察察到到SbF5超超酸酸R2CHR3C1o2o3oCH3sp2 雜雜化化平平面面型型RCH229RHRH+RR+e 鍵鍵離離解解能能 電電離離能能RHRH+e 3o2o1oCH3PhCH2CH2=CHCH2 H (KJ/mol)1

9、3161130100010719701040 3o2o1oCH330CHRCH2RRCCH p31CHRORCHRORCHXRCHXRppppCHCHHH2CH pCHHH p32（誘導）吸CCF3CCCl3CCOCNO233CCH2HHH3CH2CCCH2H3CH2CHHHCCH2HH3CH2C H34CCH2CH3HH3CH2CCCH2H3CH2CCH3H HCCHCH3CH3CH3H3C CH3CCHCH3CH3CH3H3C35CH3CH2Br+NaOHCH3CH2OHNaBr+ 希望通過這些例子，學習并基本掌握反應機理的表達方法CH3CH2BrOHCH3CH2OH+Br36CH3CBr

10、CH3CH3+H2O乙乙醇醇CH3COHCH3CH3HBr+CH3CBrCH3CH3CH3CCH3CH3H2OBrCH3COHCH3CH3CH3COHCH3CH3+HBrHBr37CCH2BrCH3CH3H3CCCH2OC2H5CH3CH3H3CC2H5OHCCH2CH3CH3OC2H5H3C+AgNO3 CH3CCH2CH3CH3H3CBrCCH2CH3CH3H3C AgBrCCH2CH3CH3H3CC2H5OHCCH2CH3CH3H3CC2H5ONO3CCH2CH3CH3OC2H5H3C HNO3HAgNO3C2H5OHCCH2OC2H5CH3CH3H3C38鹵代烷的類型和命名（掌握）鹵代

11、烷的親核取代反應，各種取代產物的類型（熟記）親核取代反應的兩種機理SN1和SN2機理（掌握兩種機理的表達方式，掌握兩種機理在反應動力學和立體化學上的不同之處）正碳離子，正碳離子的穩(wěn)定性，正碳離子的重排（掌握）39C HCClClClClClDDT40CH3CH2CH2CH2Br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異異丁丁基基溴溴異異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 bromideCHCl341HCNOFClBrISP2.12.53.03.54.02.12.53.02.82.5CX CF3CCl3 ,（強強）吸吸電電子子基基團團(electron withdrawinggroup)CRC Cl CRCClClCl 4243動力學證據動力學證據反應速率反應速率立體化學證據立體化學證據對手性底物，