第四章炔烃和二烯烃讲解课件.ppt

1、 YULIN NORMAL UNIVERSITY YULIN NORMAL UNIVERSITY YULIN NORMAL UNIVERSITYCCHH YULIN NORMAL UNIVERSITYCH2CH CH2C CHBr220CH2CHCH2CCHBr Br YULIN NORMAL UNIVERSITY例：例：YULIN NORMAL UNIVERSITYCH3CH2CCCHCH3CH2CH3CH3CHCCH3CH(CH3)2CHCCHHCH2CCH YULIN NORMAL UNIVERSITYC CCH2CHCH2CCHCH3CH CHC CHCH3HClCCBrHCH3 YU

2、LIN NORMAL UNIVERSITYF3CCCHCH3CCCH3CH2CHCCH有微弱的酸性有微弱的酸性 YULIN NORMAL UNIVERSITYRCCHR3CHKaR3CH+pKa=logKa15.7254450 YULIN NORMAL UNIVERSITYHOHH-CCHH-CH CH2H-CH2CH3pKaNaHCCH2+110HCCNa2+H2NaNH2HCCH+HCCNaNH3+HCCH-+RCCH YULIN NORMAL UNIVERSITYRCCHNaNH2+RCCNaNH3+RCCHn-C4H9Li+RCCLin-C4H10+RCCHRMgX+RCCMgXRH+

3、RCCNaRCCLiRCCMgX，YULIN NORMAL UNIVERSITYCH3CCHNaNH2CH3CCNaC2H5-BrCH3CCCH2CH3NaNH2C2H5-BrCCNaCC-CH2CH3RCCHRCCH YULIN NORMAL UNIVERSITYHCCH2Ag(NH3)2NO3+AgCCAg2NH4NO3+2NH3+HC CH2Cu(NH3)2Cl+CuC CCu2NH4Cl+2NH3+YULIN NORMAL UNIVERSITYR3CR2CHRCH2RCCH2RCH CHHC CRHX+C CRXHHC CXXRHHHHX73%YULIN NORMAL UNIVERSI

4、TYHCCHHClHgCl2CH2CHClCH3CCHHClHgCl2CH3CCH2ClHClCH3CClClCH3CH3CH2CH2CH2CCHHICH3CH2CH2CH2CCH2I3-己炔己炔(Z)-3-氯氯-3-己烯己烯(97%)CH3CHO YULIN NORMAL UNIVERSITYHC CHH2O+HgSO4,H2SO4CHOHCH2CH3CH2CCCH2CH3HClCCCH3CH2ClCH2CH3HHgSO4,H2SO4CHOCH2HCH3CHO YULIN NORMAL UNIVERSITYCH3CCHH2OHgSO4,H2SO4COHCH3CH2CH3C CH3OC CHH

5、2OHgSO4,H2SO4COHCH2C CH3OCH3CH2CH2C CCH2CH2CH3H2OHgSO4,H2SO4CH3CH2CH2CCH2CH2CH2CH3O YULIN NORMAL UNIVERSITYR C C RBr2CCl4RC CRBrBrBr2CCl4R C C RBr BrBr BrAlR3,TiCl4HCCHHCNCH2CHCNCH2CHCNn YULIN NORMAL UNIVERSITY亲核加成亲核加成:重排重排 YULIN NORMAL UNIVERSITYCH3CH2CCCH2CH3BH3THFC CCH3CH2CH2CH3HB3H2O2OHC CCH3CH2

6、CH2CH3HOHHAcC CCH3CH2CH2CH3HHCH3CH2CH2CCH2CH3O重排重排RCH2CHO YULIN NORMAL UNIVERSITYRCCHBH3,THFC CRHHB3H2O2OHC CRHHOHRCCHH2OHgSO4,H2SO4RCOHCH2RCCH3OHCCHH2OHgSO4,H2SO4HC CH1.BH3,THF2.H2O2,OHRC CHH2OHgSO4,H2SO4RC CHH2OHgSO4,H2SO4RCCRRC CR乙乙醛醛乙乙醛醛醛醛酮酮酮酮酮酮1.BH3,THF2.H2O2,OH1.BH3,THF2.H2O2,OH相同点：不同点：RCCR1.O

7、32.H2ORCOOHRCOOH+YULIN NORMAL UNIVERSITY1.KMnO42.H2OHCCHCO2+H2ORCCR1.KMnO42.H2ORCOOHRCOOH+CH3CH2CH2CH2CCH1.O32.H2OCH3CH2CH2CH2COOHHCOOH+Pd,CaCO390%CH3CH2CCCH2CH3Pd,CaCO3H2CCCH3CH2CH2CH3HH YULIN NORMAL UNIVERSITY硼化镍硼化镍 YULIN NORMAL UNIVERSITYCH3CH2CCCH2CH3H2C CCH3CH2CH2CH3HHCH3CH2C CCH2CH3Na液 NH3C CC

8、H3CH2CH2CH3HH负离子自由基负离子自由基乙烯型自由基乙烯型自由基CCRRHCCRRH反式反式稳定稳定顺式顺式乙烯型自由基乙烯型自由基反式烯烃反式烯烃乙烯型负离子乙烯型负离子CC RRNaCCRRNaNH3CCRRH YULIN NORMAL UNIVERSITYC CRRHNaC CRRHNH3C CRRHH YULIN NORMAL UNIVERSITYC CH3CHHC CH3CHCH3CH3CCCH30(BH3)3CH33B03CH3COOH通常试剂不能用硼化氢，易生成偕二硼烷。通常试剂不能用硼化氢，易生成偕二硼烷。YULIN NORMAL UNIVERSITYC CH3CHC

9、H3CC H0HBCH(CH3)CH(CH3)22硼 烷 试 剂硼烷试剂=HBCH(CH3)CH(CH3)22H2O2OH/H2OCH3CH2CH=ORCCHHHHBHB YULIN NORMAL UNIVERSITYHCCH4Ni(CN)4环辛四烯环辛四烯2 HCCHCu2Cl2NH4ClCH2CCHCH乙烯基乙炔乙烯基乙炔邻二卤代烷邻二卤代烷偕二偕二卤代烷卤代烷乙烯式卤代烃乙烯式卤代烃强碱强碱,高温高温NaNH254%YULIN NORMAL UNIVERSITYRCHXCH2XRCH2CHX2RCHCHX-HClRCCH-HClCH3(CH2)7CHCH2BrBrNaNH2H2OCH3(

10、CH2)7CCH(CH3)3CCH2CHCl2NaNH2H2O(CH3)3CCCH90%NaNH2CH3CCHCH3CCNaCH3CH2BrCH3CCCH2CH3 YULIN NORMAL UNIVERSITYCH3CH2CHCHCH2CH3Cl ClKOH,90丙醇CH3CH2CHCHCH2CH3ClCH3CH2CCCH2CH3NaNH2RCH2CH2OHRCH CH2RCHCH2XXX2RCCHNaNH2Al2O3NaNH2CCRRHHCl2Pd,CaCO3H2CCRRHH YULIN NORMAL UNIVERSITYCCRRHHCCRRHH1、C C CH3CH3HCH3BrCH3HB

11、r2、YULIN NORMAL UNIVERSITYCC CH3CH3Na液 NH3Br2HCH3BrCH3HBrCCCC例：例：CH2CHCHCH2CCCH2CCnn1 YULIN NORMAL UNIVERSITY YULIN NORMAL UNIVERSITYCH2CH CH CH2CH2CCH2C C CHC CCH3C CCH3HHH(2Z,4E)-2,4-己二烯己二烯HCCCH3CCCH3HHH YULIN NORMAL UNIVERSITY YULIN NORMAL UNIVERSITYCH2CH CH2CH CH2CH3CH2CH2CH CH2 YULIN NORMAL UNI

12、VERSITYCH3CH2CH CH2CH2CHCHCH2CH2CHCHCH21234 YULIN NORMAL UNIVERSITY1234CCCC1,3-丁二烯的模型如下图：丁二烯的模型如下图：3444A、B、YULIN NORMAL UNIVERSITYCH2CHCHCH2CH2CH CH2CH2CHCl3233C、D、34 YULIN NORMAL UNIVERSITYCH2CH2CH2 CH2CH CH2CH2CHCH2CH2CHCH2CH2CHCH2HCCHCH2HHCH3CCH3CH3CH3CCH3CH3CH3CCH3CH3例：例：CCCCClC1:C2:C3:YULIN NOR

13、MAL UNIVERSITYCH2CHCHCH2 电子衍射光谱法测定电子衍射光谱法测定C2-C3键长比普通键长比普通C-C单键键长单键键长短，具有双键的性质，即短，具有双键的性质，即电子发生了离域。电子发生了离域。CH3COO YULIN NORMAL UNIVERSITYCH3COOCH3COO12 YULIN NORMAL UNIVERSITYCH3COOCH2CHCH2CH2CHCH2CH2CHCH2CH2CH2CH2 YULIN NORMAL UNIVERSITYCH2CH CH2CH2CH CH2例：例：CH2CHOHCH3CHO YULIN NORMAL UNIVERSITYCH2

14、CHCH2CH2CH CH2CH2CHCOCH3CH2CHCOCH3CH2CHCH2CH2CHCH2CH2CH CH CH2CH2CH CH CH2CH2CH CH CH2 YULIN NORMAL UNIVERSITY贡献较小贡献较小较稳定（八隅体）较稳定（八隅体）贡献较大贡献较大贡献较小贡献较小贡献较大贡献较大较稳定（无电荷分离）较稳定（无电荷分离）贡献较大贡献较大贡献较小贡献较小 YULIN NORMAL UNIVERSITYH2C OHH2C OHCH3CHClCH3CHClCH3COOHCH3COOH贡献较小贡献较小较稳定（较稳定（N的电负性比的电负性比C大）大）贡献较大贡献较大OC

15、H3HEOCH3HEOCH3HEOCH3HE较稳定较稳定 YULIN NORMAL UNIVERSITYCH2N NCH2N N较稳定较稳定12OCH3HEOCH3HEOCH3HE YULIN NORMAL UNIVERSITYCH2CH ClCH2CH ClCH2CHCHCH2BrBr1,2-加成加成1,4-加成加成 YULIN NORMAL UNIVERSITYCH2CH CH2HCCH2CH2CH CH2HCCH2BrBrBr2Br2CH2CHCH2CHCH2BrBrBrBrCH2=CH-CH=CH2Br2CH2CH CHCH2BrBr+1,2-加成加成1,4-加成加成符合马氏加成规则符

16、合马氏加成规则1,2-加成加成1,4-加成加成 YULIN NORMAL UNIVERSITYCH2CH CH CH2HXCH2CH CH CH2HX+CH2CH CH CH2HXCH2CH CH CH2HXCH2CHCH CH2HX+CH2CHCHCH2HCH3CHCHCH2X YULIN NORMAL UNIVERSITYH2CCHCHCH2+Br2CH2Br CH CHCH2CH2Br CHCHCH2BrBrCH2Br CHCHCH2BrCH2Br CH CHCH2BrCH2CH CH CH2HBrCH2CH CH CH2HBrCH2CH CH CH2HBr+-80 C产率40 C产率8

17、0%20%20%80%YULIN NORMAL UNIVERSITYCHOCORCOORCNNO2 YULIN NORMAL UNIVERSITY1,3-丁二烯丁二烯丙烯醛丙烯醛双烯体双烯体亲双亲双烯体烯体4-环己烯基甲醛环己烯基甲醛+100 C苯OOOOOOCHO+100 C苯CHO YULIN NORMAL UNIVERSITY内型内型外型外型新形成的新形成的键与氧桥离得近键与氧桥离得近OOO+OHHOOOOOHH+COOCH3H3COOCCOOCH3COOCH3+COOCH3COOCH3COOCH3COOCH3 YULIN NORMAL UNIVERSITY YULIN NORMAL U

18、NIVERSITY内型产物：内型产物：+COOHCOOHBr2NaNH2Na,NH3(l)YULIN NORMAL UNIVERSITYCCHOOCHHCOOHCH2CHCHCHCH2CH2CH2CHCHCO2CH3 YULIN NORMAL UNIVERSITYCO2CH3COOCH3 YULIN NORMAL UNIVERSITY YULIN NORMAL UNIVERSITYCCX-O -S -Se -Te YULIN NORMAL UNIVERSITYCCCO YULIN NORMAL UNIVERSITY+Br2-8040BrBrBrBr1,2-加 成 产 物1,4-加 成 产 物(速 率 控 制 产 物)(平 衡 控 制 产 物)YULIN NORMAL UNIVERSITYCH3CCHH2Lindlar PdCH3CH CH2NBSCH2CH CH2BrCH3MgBrCH3CH2CHCH2CH3CH2CH2COCH3CH2CCHCH3OOCOHOH;.YULIN NORMAL UNIVERSITY