有机化学课件：第三章 不饱和烃

1、12CCCCHCCHCCHHHH3456789101112CH3CH2CH2CCHCH3CHCCHCH3CH3CH2CCCH3CCHHHCH2CH3CCHCH3HCH3CH3CHCHCH313CCH3CHHCH3CCH3CHHCH3CH3CHCHCH31415常见的烯基和炔基：常见的烯基和炔基：乙烯基乙烯基 (vinyl)烯丙基烯丙基(allyl 或或allylic group)CH3CHCHCH2CHCH2CHCH2丙烯基丙烯基 (propenyl)CH2CCH3异丙烯基异丙烯基 (isopropenyl)CHCCCH3CCCH2HC乙炔基乙炔基(ethynyl)炔丙基炔丙基 丙炔基丙炔基

2、16RHRYCH3CHCH2(CH3)2CCH2CH3CH2CCCH3(CH3)2CHCCH17CCCH3CH2CH3CH2CH2HHCH3CCH3CH3CHCHCH3CH3CH2CH31 12 23 34 4CH3CH2CH31 12 23 34 41 12 23 34 418CCHCH2CH2CH3H3CCH3CCHCH2CH2CH3H3CCH3CH3(CH2)3CHCH(CH2)4CH3CCH2CH3CH3CCCH319CCClHBrCH2CH3CCClBrHCH2CH320 如果直接相连的第一个原子相同，继续如果直接相连的第一个原子相同，继续 逐个比较与双键逐个比较与双键C原子相距的第

3、二个、第三个原子相距的第二个、第三个原子的原子序数。原子的原子序数。(Z) 3甲基甲基2己烯己烯反反3甲基甲基2己烯己烯Z或或E式与顺或反式式与顺或反式没有相关性没有相关性CHHHCCHHHHHCHHHCCHHHHHOHCHHHOOHCHHHO RCHCH2RCHCHRR2CCH2 R2CCHR R2CCR2RCCH RCCRHCCCCHCH2CH2OHCH3PdC CaCO3+ H2喹 啉 80%H2CCHCCHCH2CH2OHCH327C CC CC CH HCCH28CC+ H2C CH H29CCHHCH3CH3CCHHCH3H3C30CH3CH3H2, PtCH3CH3HHCH3CO

4、OHN31(100%)CH3(CH2)3CC(CH2)3CH3H2LindlarCH3(CH2)3CC(CH2)3CH3HH催催化化剂剂NiOCCH3ONaBH4C2H5OH2Ni2BCCCCHHRRH2P2RR。CCCH3CH2C CCH2CH3Na/NH3(液)(或)Li/NH3(液) 。CH3CH2C CCH2CH3HH/7878/以上反应说明以上反应说明炔烃加氢炔烃加氢比烯烃加氢来得比烯烃加氢来得容易。容易。3233CC34CC(CH3)2CHCHCHCH3+ Br2CCl4(CH3)2CHCHCHCH3BrBrB rB r CCBr + BrCC35CCBrBrCCBrBrBrBrB

5、rHHBrBrH BrH363738H2CCH2CH3CHCH2(CH3)2CCH2(CH3)2CCHCH3(CH3)2CC(CH3)2H2CCHCOOHH2CCHBr46Cl-CCH2CH3CH3HClCl-CCH2CH3CH3HClCCH2CH3CH3H+CCH2CH3CH3+HCCH2 + H ClCH3CH347+CH3C=CHCH3+CH3CH3C CHCH3CH3ClI(H)BrI Cl(HBr)( )+Cl3C CH CH2HBrCl3C CH2 CH2Br+48CH3CHCH3CH CH2HHClCl-(I)Cl-C+的稳定性的稳定性:叔碳正离子叔碳正离子仲碳正离子仲碳正离子(

6、II)氢迁移氢迁移 CH3CCH3CH2CH2H思考题思考题 给出下列反应的机理：给出下列反应的机理： + HBrCH2CH3Br(40%) (60%)CH3CHCH3CHCH2HCl(CH3)2CHCHCH3Cl+ (CH3)2CCH2CH3Cl0(f) 碳正离子的重排：碳正离子的重排： 49H2CCHCH2CH3+ HBrBrCH2CH2CH2CH3(95%)ROORCH3COOPhCOCPhOOOOCCH3OROOR :50CH3CH2CH=CH2+HBrCH3CH2CH2CH2BrROOR+ROORROROHBrROHBr.2hv链 引 发BrBrBr BrBrCH3CH2CHCH2B

7、rCH3CH2CHCH2Br.+BrCH3CH2CHCH2BrCH3CH2CHCHCH2CH3CH2BrCH2Br链终止.+BrCH3CH2CH CH2CH3CH2CHCH2BrCH3CH2CHCH2BrHBrCH3CH2CH2CH2BrBr.链传递51CH2=CH2H2SO4CH3CH2OSO3HH2OCH3CH2OH909098%。CC。%603025。CCH2SO4CH3C CH2CH3 C CH3CH3 C CH3CH3CH3CH3OHOSO3HH2OCH3 CH CH2H2SO4CH3CHCH3H2OCH3CHCH3OH5050。CC%80OSO3HCH3CH=CH2+HOSOH50

8、OOCH3CHCH2H-OSO3HCH3CHCH3OSO3HH2OCH3CHCH3OH+-5253CC+CCXX2 + H2OOH+ HXCH3CH2CHCl2H2OCH3CH2ClCCH3CH2CHClOHHH+54CC+HHHHH2OH2SO4(cat.)CH3CH2OH250 CCH2=CH2+H+CH3CH2H2O.CH3CH2H+OH2CH3CH2OH+55keto-enol tautomerism)CH3(CH2)3CCH+H2OHgSO4H2SO4CH3(CH2)3C=CHOHHCH3(CH2)3CCH3OCCOHCCOHC CCOH(R)56/CH2=CHCH2CH2OHgSO

9、4/H2SO4CH2=CHCH2COOHH2O H2SO4CH3CHCH2CCHCHCH357CH3(CH2)7CHCH2CH3(CH2)7CH2CH2OHCC+BHCCHBB2H6 + OOBH358CH3CH2CH+BH2H-CH3CHCH2BH2HCH3CHCH2(CH3CH2CH2)2BHCH3CHCH2(CH3CH2CH2)3B(CH3CH2CH2)3BH2O2OHCH3CH2CH2OH59CH3CHCH=CCH3CH3OH重排CH3CHCH2CCH3OCH3(CH3)2CHC C CH31225(BH3)2醚CH3H2O2NaOH/H2O。CC/H25(H)(H)/C=C(CH3)

10、2CHBH260CHHCH3COOHCH3 CHCH3C CCH325。(CH3)2CHC C CH31225(BH3)2醚CH3。C/H(H)(H)C=C(CH3)2CHBH2炔烃硼氢化反应再质子化被还原为顺式烯烃。炔烃硼氢化反应再质子化被还原为顺式烯烃。61CC+ H BrCCBrHCC+ Br BrCCBrBrCH3+ B2H6HH2BCH3HH2O2OHHHOCH3H1262CH3(CH2)2CH CH2(AcO)2Hg, THF-H2O-AcOHCH3(CH2)2CH CH2HOHgOAcNaBH4NaOH, H2OCH3(CH2)2CH CH3HO+ Hg + AcOH63HCCH

11、 + CH3OH20% KOH160165 C22.5 MPaH2CCHOCH3HCCH + CH3COOHZn(OAc)2/活活性性炭炭170230 CH2CCH OCCH3O64HCCHCH3OHCCHOCH3CH3OHCH3OH2CCHOCH365CC+ RCOOOHCC+ORCOOHCH3COOOH66冷冷稀 KM nO4OOM nOOHHKOHH2OHOOHHH(CH3)3COOH, OsO4 (cat)(CH3)3COH, HOHOHOHH67CH3CH2CHCHCH2CH3+ KMnO4H2OCH3CH2CHCOCH3+ CO2OH(45%)CCH3CH3+ KMnO4H2OO

12、+ OCH3CH3CHRRCOOHR1R2CR1COR268CCRCRCOOHCHCO2 + H2OCH3CH2CH2CH2CCH H+ KMnO4, HOCH3CH2CH2CH2COOH+ CO2 + H2OCCO3CCOOO重重排排CCOOOH2OZnCO + OC69CCH3CH3CHCH31) O32) H2O, ZnCCH3CH3O + OCCH3HCCHR O3RCOH+ CO2O H2O70H2CCH2+ O212PdCl2C CuCl2H2O120130 C0.4 MPaCH3COHH2CCH2+ O2Ag280300 C12 MPaH2CCH2O1271n CH2CH2200

13、 , 200MPaO2 或 过 氧 化 物 CH2CH2( )nCCH2H3CH3C+ H2CCCH3CH350% H2SO4+H3CCH3CCH3CHCCH3CH3(80%)H3CCCH3CH3CH2CCH3CH2(20%)72CHHCCuClC NH4ClH2CCHCCCHCH2CHCuCl2C NH4Cl8084 CH2CCHCCH2 HCH2CCCH3CH3H+H3CCCH3CH3H2CCCH3CH3H3CCCH3CH3CH2CCH3CH3H3CCCH3CH3CH2CCH3CH3H+H3CCCH3CH3CH2CCH3CH2H3CCH3CCH3CHCCH3CH373H2CCHCHHHnC

14、H3CHCH2TiCl4Al(C2H5)350, 2MPaCH3CHCH2( )n74CH3CHCH2Cl2500510 CClCH2CHCH2+ HCl(75%80%)ClCl高高温温2 ClCl + CH3CHCH2CH2CHCH2+ HClCH2CHCH2+ Cl2ClCH2CHCH2+ Cl75+OON BrCCl4Br+OON H(82%87%)76HCC H2CCH H3CCH2CCHHKaCCH+ H77HCCHH2CCH2CH3CH3HF HOH ORHCCRHNH2HHCCH+ Na NH2 NH3(液)CCHNa+ NH378CCNaNaR ClCCNaRR ClCC RRRXRCH2Cl+Pd/CaCO3HBrCH3CH2BrHCCHH2CH2=CH2(AcO)2Pb+220。CNaCCNaHCCHNa279CCHCH3CH2CCH + Ag(NH3)2NO3CH3CH2CCAg+ NH4NO3 + NH3+2CH3CH2BrNaCCNa33。C液氨CH3CH2CCCH2CH3H2/Pd/BaSO4CH3CH2CH=CHCH2CH3CH3CH2CH2CCH2CH3OH2O/HgS