有機(jī)化學(xué)課件：第三章 不飽和烴

1、12CCCCHCCHCCHHHH3456789101112CH3CH2CH2CCHCH3CHCCHCH3CH3CH2CCCH3CCHHHCH2CH3CCHCH3HCH3CH3CHCHCH313CCH3CHHCH3CCH3CHHCH3CH3CHCHCH31415常見的烯基和炔基：常見的烯基和炔基：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異丙烯基異丙烯基 (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 如果直接相連的第一個原子相同，繼續(xù)如果直接相連的第一個原子相同，繼續(xù) 逐個比較與雙鍵逐個比較與雙鍵C原子相距的第

3、二個、第三個原子相距的第二個、第三個原子的原子序數(shù)。原子的原子序數(shù)。(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式與順或反式式與順或反式?jīng)]有相關(guān)性沒有相關(guān)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催催化化劑劑NiOCCH3ONaBH4C2H5OH2Ni2BCCCCHHRRH2P2RR。CCCH3CH2C CCH2CH3Na/NH3(液)(或)Li/NH3(液) 。CH3CH2C CCH2CH3HH/7878/以上反應(yīng)說明以上反應(yīng)說明炔烴加氫炔烴加氫比烯烴加氫來得比烯烴加氫來得容易。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+的穩(wěn)定性的穩(wěn)定性:叔碳正離子叔碳正離子仲碳正離子仲碳正離子(

6、II)氫遷移氫遷移 CH3CCH3CH2CH2H思考題思考題 給出下列反應(yīng)的機(jī)理：給出下列反應(yīng)的機(jī)理： + HBrCH2CH3Br(40%) (60%)CH3CHCH3CHCH2HCl(CH3)2CHCHCH3Cl+ (CH3)2CCH2CH3Cl0(f) 碳正離子的重排：碳正離子的重排： 49H2CCHCH2CH3+ HBrBrCH2CH2CH2CH3(95%)ROORCH3COOPhCOCPhOOOOCCH3OROOR :50CH3CH2CH=CH2+HBrCH3CH2CH2CH2BrROOR+ROORROROHBrROHBr.2hv鏈 引 發(fā)BrBrBr BrBrCH3CH2CHCH2B

7、rCH3CH2CHCH2Br.+BrCH3CH2CHCH2BrCH3CH2CHCHCH2CH3CH2BrCH2Br鏈終止.+BrCH3CH2CH CH2CH3CH2CHCH2BrCH3CH2CHCH2BrHBrCH3CH2CH2CH2BrBr.鏈傳遞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炔烴硼氫化反應(yīng)再質(zhì)子化被還原為順式烯烴。炔烴硼氫化反應(yīng)再質(zhì)子化被還原為順式烯烴。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 過 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高高溫溫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