炔烃的化学性质一课件.ppt

1、 本节重点本节重点 sp杂化轨道杂化sp激发能量2s2px2py2pz2s2px2py2pz 2pz2py基态 激发态 杂化态CCHHCC HH0.12nm0.106nmCCCCCC0.146nm0.121nm0.134nm CH3CH2CCHC CCH3CHCH3CH3CCHCCHCH2CH2CH CH2CCHCH3CH CHCCH（两种编号中一种较高时，宜取低。）CH2CCHCH3(CH3CH2CH2)2CHCCCH3 RCCHH2催化剂RCHCH2 催化剂H2RCH2CH3CH3(CH2)2CC(CH2)2CH3H2林德拉催化剂，CH3(CH2)2CHCH(CH2)2CH3R CCHX2

2、R CHCHX2R CCHXXXXXXCH3CCCH3Br2,乙醚-20CCCH3BrBrCH3Br225CH3CHBr2CHBr2CH3CH3CC H+2Cl2CH3CCl2CHCl2 1,1,2,2-四氯丙烷四氯丙烷 63%n-Bu C C H+Br2+BrBrHn-BuBrHBrn-BuCH3CO2H.H2O 28%72%CH3CCHHICH3CCH2IHICH3CCH3IICHCH+HClHgCl2150160CH2CHClR C CHR C CH2XCXXRCH3HXHXR CCH2R CH CH+（解释）CH2CHCH2CCH+（炔烃SP杂化的原因）Br2CH2BrCH CH2C

3、CHBrR C CHR CCH2O-HCORCH3+OH2HgSO4H2SO4（符合马氏规则）H+R CCH2+OH2R CCH2OH2+-H+CC-OHCHC O 烯醇式烯醇式 酮式酮式CHCH+H2OCH2C OHHH2SO4,Hg2+100CH3OHCH3(CH2)5CCH+H2OH2SO4,HgSO4COCH3(CH2)5CH3 91%CHCH+HCNCH2CHCNCu2Cl2_NH4Cl R CCHRCOKOKMnO4 R CC RRCCOORH2OH2O2RCOOHRCOOH+O3H CC H银氨溶液Ag CC Ag+NH4NO3（白色）（2AgNO3+2NH4OH）R CC HR

4、 CC Cu铜氨溶液+NH4Cl（棕红色）(CuCl2+2NH4OH)R C CH+M+R CCHM+R C CM+H+R C CHR C CNaNaNH2CH3XR CC CH3-+CHCCH2CHCH3CH2 CHCCH2CHCH3CH2 H2C CH2 H3C CH3pKa 25 44 50 R C C RPd/CaCO3+2H2CH2CH2RR（未毒化）R CCRRCCRHHH2Pd/CaCO3（喹啉毒化）Lindlar CatalgstCH3(CH2)3C C(CH2)3CH3+H2CC(CH2)3CH3CH3(CH2)3HHLindlar Pd R CC RNaNH3RCCRHH氢

5、化铝锂在二甘醇二甲醚存在下也可还原炔烃为反式烯烃：氢化铝锂在二甘醇二甲醚存在下也可还原炔烃为反式烯烃：CH3CH2CCCH2CH3+LiAlH4CH3CH2CCCH2CH3HHTHF,diglyme138odiglyme:(二甘醇二甲醚）CH3CHCH2ClClKOHNaNH2CH3CHCHClCH3CCHCH3(CH2)7CHCH2BrBrNaNH2CH3(CH2)7CCH R CCLiRXR CC RR CCH+BuLi CHCCH2CH3H3C CCCH2CH3CHCH1.NaNH22.CH3Br1.NaNH22.CH3Br81%CCH(CH2)n CHCCCCCCCC CCCCCH3C

6、H3CH2CH3HHH(2Z,4E)-3-甲基-2，4-庚二烯CCCHHHH+-sp2spsp2 CH2CCH2CH3CCH2OHCH3C CH3OH2O,H+(CH3)2CCCH2CCH(CH3)2CHKOH,C2H5OH3-甲-1-丁炔3-甲基-1，2-丁二烯异构化化合物氢化热CH3CH2CH CH2H2CCH CHCH2CH3CH2CHCH CH3CH2CH CH CHCH3CH2CH CH2CH CH2CH2CH CH2CH2CH CH2126.8115.6238.9226.4254.4253.1 C=C 0.133nm :C-C 0.1534nm E*43*21-+-1.618-0.

7、618+0.618+1.618(原子轨道能量)-+-+-+-+-+-+4321 -：CH2CHCHCH2CH2CHClCH2CHCH2CH2CHCH2CH2CHCH2CH3CHCH2(CH3)3C+-p-：-：-P:超共轭效应CH2CHCH2CH2CHCH2CH2CHCH2+-在，中 CH2CHCH2CH2CHCH2CH2CH CH2+-E3*21-+-+-1.414+1.414(反键轨道)(非键轨道)(成键轨道)CH2CHCH2CH2CHCH2CH2CHCH2+-CCHHHHH+CH2CH CH CH2Br2ClHH2CH CHCH2CH3ClCH CH CH2ClCH3CH2CH CH2CH3CHCHCH3CH3+CH2BrCHCH CH2BrH2CBrCH CH CH2BrE1,2加成反应进程1,4加成反应进程E1E21，2-加成产物1，4-加成产物反应物 +OOOOOO双烯体亲双烯体苯，1005h90%+CH2CHOCHO+CO2MeCO2MeCO2MeCO2Me+MeO2CCO2MeCO2MeCO2MeCHOCOROCROCNNO2