第08章卤代烃

1、Chapter 8Chapter 8主要讲授内容主要讲授内容Chapter 8Chapter 8官官能能团团(Ar) RH(Ar) RXX种类：种类： RF、 RCl、 RBr、 RI Chapter 8烯丙基氯烯丙基氯Chapter 8CH CH2CCH3CH3CH3H3CCH3RCH2XR2CHXR3 CX1 1O O卤卤代代烷烷2 2O O卤卤代代烷烷3 3O O卤卤代代烷烷Chapter 8卤原子卤原子电负性电负性*F4.0Cl3.0Br2.8I2.5CXsp3 Chapter 8CHRCH Cl BaseNuCRCCHRCNuNuBChapter 8Chapter 8Chapter

2、8 卤烃的相对密度取决于分子的相对分子质量和卤卤烃的相对密度取决于分子的相对分子质量和卤素种类。素种类。 R-F、R-Cl d 1 同一卤素同一卤素，C数数 ，d RXn ，n ， d 1 d 1Chapter 8Chapter 8CH3CH2CH2Cl H :1.061.813.47CH3X: H :CH3FCH3ClCH3BrCH3I4.263.052.682.16Chapter 8Chapter 8RCH2X+RCH2X+-NuRCH2NuX-Chapter 8.CINaOHOHNaClH2O+RCH2X+RCH2OHHX.H2O+NaOHRCH2OHNaX+RCH2X+.H2OChap

3、ter 8RX.HOR+RORHX+RXNaOR+RORNaX+.H2ORXNaSR+RSRNaX+CH3CH CH2OHCa(OH)2H3C CH CH2OHCl+ClHOCH2CH2ClClCH2CH2OHNaOHH2CCH2OCH2H2CO+ HClChapter 8RX.NH3+RNH2HX+.RNH3XRNH3XNaOH+H2ORNH2NaX+.+RNH2RXR2NHRXR3NRXR4NX123季季铵铵盐盐Chapter 8n - C4H9Br + NaCNn - C4H9CN + NaBrRX +CROROCRONa ONaX+RX +Na CNaX+CRCCRRChapter 8

4、硝酸酯硝酸酯RXRONO2Ag ONO2AgX+C2H5OH CH2=CHCH2X C6H5CH2X C6H5X Chapter 8Chapter 8 Chapter 8NuX底底物物 substrate负负离离子子型型分分子子型型RXRNu+HXRNu+NuHRXOH+ROHX+.H2OChapter 8HO + H3CBrCH3OH +BrH2O = kCH3BrOHChapter 8Chapter 8 HO + H3CBrCH3OH +BrH2O = kCH3BrOHChapter 8XR HO HORX 过过渡渡态态OHRX+OHRX+HORX XR+Ereaction progres

5、s HOEarHm = kRXOHrHm旧键断裂和新键形成旧键断裂和新键形成同时进行，一步反应同时进行，一步反应Chapter 8HO+-CBrH13C6H3CH+CHOC6H13CH3HBr-SN2(S)(+)2溴辛烷(R)()2辛醇 = +34.25 = 9.90- 2= sp3CRCXRNuCRRNu+RHspXNuH- RHChapter 8 = k RX OH OH-CH3HHBrH3CHHOH+SN2+Br- (CH3)3CBrOH+(CH3)3COH + BrChapter 8Chapter 8XRRNuNuRX+慢慢快快 = k RX rHmOHRRX XREreaction

6、progress HOEa +RrHmaE21 R +Ea1Ea2Chapter 8R1CR2XR3Nu2CRspXHRNuaabbR1CR2NuR3R1CR2NuR3+Chapter 8CH3BrCH3HCH3HCH3H2OHH2OBrOHCH3CH3HCH3OHCH3H(Z)(E)CHOH2OClHPhH3CCOHHPhH3C+CHOHPhCH3(S)(S)(R)(49%)(51%)Chapter 8H2OBrOH2oHHO3o = k RX Chapter 8Chapter 8RBr + H2OR OH + HBrCH3COOHSN1 R: (CH3)3C- (CH3) 2CH- CH3

7、CH2- CH3-相对速率：相对速率： 1.2106 45.00 1.70 1.00RBr + NaIR I + NaXCH3COCH3SN2 R: (CH3)3C- (CH3) 2CH- CH3CH2- CH3-相对速率：相对速率： 0.001 0.01 1.00 150Chapter 8RRXRNuRRR+碳正离子RRXR X+Chapter 8 NuXRNuRX过渡态 NuRXChapter 8Chapter 8CCHHNuXCCCH3- - HHHHHH= Chapter 8Cl7, 7- -二二甲甲基基- -1- -氯氯二二环环2.2.1庚庚烷烷30% KOH, 21 hEtOH,

8、AgNO3, 48 hSN2反反应应条条件件SN1反反应应条条件件不不反反应应+ClOH构构型型无无法法翻翻转转难难解解离离SN2难难不不能能形形成成平平面面SN1难难ClChapter 8RX+RX+RX-Chapter 8离离去去能能力力强强弱弱SN1SN2Chapter 8 = k RX Nu 0 = k RX Nu RX Chapter 8C2H5O- HO- CH3CO2- C2H5OH H2OR3C - R2N - RO- F - NH3 H2OI - Br - Cl- F - HS - HO - Chapter 8.XHORH ORHORO HR-F CI Br I F CI B

9、r I Chapter 8OCCH3CH3H3COCCH3H3COCH3COC亲亲核核性性强强强强弱弱弱弱碱碱性性烷烷基基给给电电子子作作用用试试剂剂的的体体积积作作用用HHHHHHChapter 8 NuCX RHHChapter 8CBrHCH3COOH2O+COHCH3CHOHO+BrChapter 8CBrHCH3COOCBrHCOCH3O BrCCH3HCOOH2OCOH2CHCH3OOCCHOH2H3COOHCOHCH3CHOO-O-, -OH, -OR, -OCOR, -NR2, -SH, -SR, -X, -ArChapter 8Chapter 8Chapter 8CHCX B

10、CC+碱X+HBC2H5OH酸酸性性EliminationChapter 8+C2H5ONaCHCH3HCHHX C2H5OHE2SN2C2H5OCH2CH2CH3+ NaBr91%CH3CHCH2+ NaBr+ C2H5OH9%Chapter 8 CCHXB+BHCCHXB +X过过渡渡态态快快慢慢CCB = OH, OR反反应应进进程程SPTSEChapter 8+C2H5OHCCH3CH3H3CBr 25 COCH3CCH2CH3+CCH3CH3H3COCH2CH3 81%19%Chapter 8Chapter 8CCHXCCH- - XB CC+BH慢慢快快反反应应进进程程SPETS1

11、TS2MChapter 8CCH3CHCH3BrCH3H3CEtOHCCCH3CH3H3CCH3+CCHCH3CH3H2CCH3Chapter 8CCH3CHCH3BrCH3H3C- BrCCH3CHCH3CH3H3C CH3CH3 迁迁移移CCCH3CH3H2CCH3H BrCCCH3CH3H3CCH3H BrC CHCH3CH3H2CCH3abEtOHChapter 8CH3CHCHCH2HBrHKOH CH3CH2OH70 COCH3CHCH CH3CH3CH2CH+CH219%81%Chapter 8CH3CH2CBrCH3 EtOHNaOC2H5CH325 CO+CH3CH2CCH2

12、CH3CHCCH3CH3CH3+80%20%CHCHCHCHCHHBrH CH3 EtOHCH2CH3主主要要产产物物Chapter 8CH3CHCH CH3CH3CH2CH+CH253%47%BrCH3CH2CHCH3KOC(CH3)3HOC(CH3)3 ,HHCH3BrH3CHHHHBrHC2H5OO较较拥拥挤挤位位阻阻大大，动动力力学学不不利利较较宽宽松松位位阻阻小小，动动力力学学有有利利VsChapter 8CH3CH2CH2CH2CHCH3NaOCH3HOCH3+F CH3CH2CH2CH2CHCH2+ CH3CH2CH2CHCHCH370%30%(CH3)3CCH2C(CH3)2B

13、rNaOC2H5HOC2H5 ,(CH3)3CCH2 C(CH3)2+(CH3)3CCH2C CH3CH314%86%Chapter 8CH3CHCHCH2HBrHKOC2H5 / CH3CH2OH70 COCH3CH2CH+CH220%CCHCH3CH3H+CCCH3HCH3HE- - 60%Z- - 20%Chapter 8HCH3HBrH3CHOEtHHH3CBrH3CHOEtHCH3HBrH3CHOEt HHH3CBrH3CHOEt CCHCH3CH3H( E )CCHCH3HCH3( Z )空间张力空间张力Chapter 8问题讨论：问题讨论：解释解释1, 2 二苯基二苯基 1 溴丙

14、烷消除反应结果溴丙烷消除反应结果PhH3CHBrHPh PhCH3HBrHPh orKOEtEtOHH3CPhHPhPhH3CHBrHPh PhCH3HBrHPh or1R, 2R1S, 2S1S, 2R1R, 2SKOEtEtOHH3CPhHPh三三取取代代烯烯烃烃，较较稳稳定定Chapter 8ClCH3C2H5O(H3C)2HCCH3CH(CH3)2CH3+75%25%IC2H5OH(H3C)2HC稳定构象，存在反式共平面氢，能发生消除HCl(H3C)2HCHHCH3C2H5OOC2H5ababChapter 8ClCH3(H3C)2HCCH3II100%C2H5OC2H5OH(CH3)

15、2HC构象转化HCl(H3C)2HCHHCH3稳定构象不存在反式共平面氢不能发生消除(H3C)2HCClHCH3HH不稳定构象存在反式共平面氢能发生消除OC2H5Chapter 8CCXHNu- ESNChapter 8试试 剂剂 的的 碱碱 性性 与与 浓浓 度度强强弱弱反反 应应 趋趋 势势ESN+CH3CCH3BrCH3NaOC2H5HOC2H5(CH3)3COC2H5+ (CH3)2CCH2SN / %E / %NaOC2H5 / mol L 10.0065350.0254460.0844561.00 298Chapter 8SN1 & E1 机理决速步骤中间体碳正离子的生成机

16、理决速步骤中间体碳正离子的生成:R中中间间体体: : 电电荷荷集集中中XR XR+RXS So ol l. .S So ol l. .Sol.极性增强，极性增强，有利于有利于SN1 & E1反应反应Chapter 8SN2过渡态：过渡态：E2过渡态：过渡态：CCHXB NuCX Chapter 8提高反应温度，有更利于消除反应。提高反应温度，有更利于消除反应。 SNE反反应应温温度度高高CH3CH2CH2Br + NaOHH2OC2H5OHCH3CH2CH2OHCH3CH2CH2Chapter 8Chapter 8CCHHHClH2CCHClp p- - 共共轭轭体体系系电电子子效效应

17、应： C C- -C键键：电电子子云云密密度度下下降降C- -X 键键：部部分分双双键键性性质质Chapter 8H2CCHClH2CCH2CH2CHCIAgNO3+CCBrCH3CH3HCCCH3CH3KOH / C2H5OHH2CCHClabHBrH2CCH2HClH2CCHHCiH2CCHHClChapter 8XXCH2CHCH2ClCH2CHCH2Cl+CH2CH2CHCHCH2CH2 Chapter 8CH3CHCHCH2ClH2ONaOHCH3CHCHCH2ClCH3CHCHCH2+HOCHCH3CHCH2 abCH3CHCHCH2OHCHCH2CH3CHOHabCH2CH2CI

18、CH2CI-+CH2CH2CH2+ + +Chapter 8CCICH3CHCH2ClNa2CO3/H2OKOH / ROHCCICH3CHCH2OHCCH3CCH2OHChapter 8ONaNaOH / CuCINH2NH3 / Cu2O200 6MPa350 370 NH2NaNH2NH3(l) H3OOHChapter 8ONa2CO3 / H2OClNO2100 C H3OONaNO2NO2NO2OHNO2NO2ONa2CO3 / H2OClNO2220 C H3OONaNO2OHNO2BrNO2OC2H5NO2NaOC2H5C2H5OH+ Chapter 8FCINaOH+H2OO

19、HCIOHCINO2ClCINO2NaOH+H2OChapter 8ONa2CO3 / H2OClNO2220 C H3OOHNO2Nu-+ XNO2.慢慢- XNuNO2- XNuNO2-Chapter 8.XNuNO2+-XNuNO2- - 快快Ereaction progressEarHmaE21ABCDEEa1Ea2Chapter 8Cl*KNH2C 液 NH3NH2NH2(47%)- -33+(53%)*14C标记氯苯与标记氯苯与KNH2 / 液液NH3的反应的反应NH2NH3*ClH+-CI-*Cl-*+-*+-*Chapter 8*NH2-*NH2NH3*NH2NH3*NH2+N

20、H2-*NH2+NH2-CH3CICH3CH3NH2CH3NaNH2NH3+Chapter 8BrO2NICF3CF3CF3CF3O2NCu+200 COIICu+230 COClClCu+220 CONO2O2NNO2O2NChapter 8Chapter 88.6.1 多卤代烷烃多卤代烷烃8.6.2 有机氟化合物有机氟化合物Chapter 8Chapter 8(Ar) R+XMEt2O(Ar) RM+MX离子性极性、族RC-M、族碱金属过渡金属离子型极性共价键型RC-M +RC-M弱极性共价键Chapter 8ether(Ar) R+XMg(Ar) R MgXOEt2O 、Bu2O、(TH

21、F) 、C6H6Chapter 8Victor Grignard(1871 1935)Chapter 82 RMgXR2Mg+MgX2fastetherRXMgOEtEtOEtEt单单体体( (稀稀溶溶液液) )XMgXMgOR2RRR2O二二聚聚体体( (浓浓溶溶液液) )Chapter 8 RMgX2O2H2OROH+2 ROMgXROMgXOOCORMgX+ +H2ORCOOHMgBrClCH2CHCH2CH+CH2Et2OCH2RX+XMgCCREt2ORCCR+MgX2Chapter 8RMgXHOHHORHOCROHCCRHNR(H)2RHMgX(OH)MgX(OR)MgX(OCR)OCCRNR(H)2XMgXMg制备炔基Grignard试剂DODMgX(OD)RD制备氘代试剂+Chapter 8COCOMgXRCOHRRMgXH2O Et2OCO RMgX+2CdCl2R2Cd+MgXCl2RMgX+SnCl44R4Sn+MgXCl4Chapter 8CH3CH2CH2CH2CICH3CH2CH2CH2Li + LiCI2 Li+E