高四3章_不饱和烃-2

1、催化加氢 CH2=CH2 + H2CH3-CH3催化剂RCH2CH3Ni or Pd,PtRC CH + H2H2CH2=CH2H-CH2-CH2-HHHHHC2H4吸附解吸在适当的催化剂作用下，烯烃或炔烃与氢加成生成烷烃：Ni须经处理，得Raney Ni，又叫活性Ni、骨架Ni。这种镍特点是具有很大的表面积，便于反应按下列机理进行：中间形成一个Ni-H键(半氢化态)为过渡态。Cat.：Pt、Pd、Rh、Ni等。C=CHCH3CH2(CH2)3CH3HNa-液NH3-33 C。CH3CH2-C C(CH2)3CH3CH3CH2-C C-CH2CH3B2H6，醚0 C。CH3COOHC=CCH3

2、CH2HCH2CH3HC=C+ Br2红棕色无色CCl4CCBr BrRC CHRCCl=CHClRCCl2CHCl2Cl2(or Br2)Cl2(or Br2)(RCBr2CHBr2)CH2=CH-CH2-C CH + Br2CH2BrCHBrCH2C CH乙醚低温4,5-二溴-1-戊炔CH3C CCH3C=CBrCH3BrH3CBr2乙醚，-20 C。CH2=CH2 + Cl2CH2-CH2ClClFeCl3,40 C,0.2MPa1,2-二氯乙烷，97%。1,2-二氯乙烷(常用溶剂)H-C C-HCl ClCl ClCH=CHClClCH CHCl2,FeCl3,CCl480-85 C。

3、Cl2,FeCl3,CCl480-85 C。1,2-二氯乙烯1,1,2,2-四氯乙烷3-己炔反-3,4-二溴-3-己烯C2H5C CC2H5Br2，乙酸-Br-,80%C=CBrC2H5BrH5C2CCBr+C2H5H5C2Br-角张力更大，内能更高CCBrBrCCBr+烯烃慢+ BrBrC=CBr-快CH2=CH2 + Br2(Br2不裉色)CH2CH2BrBr(Br2裉色)x微量水CCl4干燥CCl4CH2=CH2 + Br2CH2=CH2CH2=CHCH3CH2=C(CH3)2CH3CH=C(CH3)21.02.035.5310.40.04CH2=CHBr烷基取代增多，双键上电子云密度增

4、大，亲电加成反应速率增大双键上电子云密度减小，亲电加成反应速率减小-Br是吸电子基!CH3-是给电子基!H2O,NaClCH2-CH2 + CH2-CH2 + CH2-CH2BrOHBrBrBrClCH2=CH2+ Br2(少量)+ H XC=C：(HX=HCl,HBr,HI)CCHXXXHXHXR-C=CH2R-C-CH3XRC CH CH3XHCH3HXH2C=CHCl氯乙烯HClH3C-CHCl2Cu2Cl2or HgSO4HgCl21,1-二氯乙烷（有机溶剂）CH CH + HClHgCl2CH3-CH=CH2 + HBrCH3CH2CH2Br主要产物次要产物CH3-CH-CH3Br+

5、C=CHX+X-HCC+X-HXCCHCC+马氏规则烯、炔加卤化氢时，氢原子总是加到含氢 多的不饱和碳上。例如：2-氯丙烷1-氯丙烷CH3-CH=CH2 + HClCH3CH2CH2Cl主要产物次要产物CH3-CH-CH3Cl+CH3CH2CH=CH2 + HBr2-溴丁烷CH3CH2CH CH2HBr80%乙酸CH3CH2CH2C CHCH3(CH2)2-C-CH3BrBrHBrHBrCH3CH2CH2C=CH2Br2-溴-1-戊烯2,2-二溴戊烷CH3-CH=CH2 + H+CH3CH2CH2Br(主要产物)(次要产物)CH3-C+H-CH3CH3CH2CH2+Br-Br-CH3-CH-C

6、H3Br()()CH3CH3C+H3C+HCH3CH3C+CH3C+H2CH3C+H33。C+2。C+1。C+ CH2=CCH3CH3+H+CH3-C+-CH3CH3C+H2-CHCH3CH3CH3-C-CH3CH3BrCH2-CHCH3CH3BrBr-Br-(主)(次)Cl说明烯烃加HX的反应确实经过碳正离子中间体!CH3-C-CH=CH2CH3HHCH3CH3-C-CH-CH3+HCH3CH3-C-CH-CH3ClHCl-Cl-Cl-2 碳正离子。1,2-氢迁移(重排)预期产物重排产物 (主)(次)HCH3CH3-C CH-CH3CH3CH3-C-CH-CH3+H。3 碳正离子Cl-CH3

7、-CH=CH2 + HBrCH3-CH-CH3Br（主）CH3-CH=CH2 + HBrhor 过氧化物CH3CH2CH2Br （反马）只能是HBr (HCl、HI都不反马) 引发R-O-O-Rh2RO过氧键+ CH3CH=CH2BrROROH + BrCH3-CH-CH2Br。1 ,不稳定。2 ,稳定CH3-CH-CH2BrCH3-CH-CH2Br + HBrCH3CH2CH2Br + Br增长+ H Br终止Br+BrBr2BrCH3CHCH2Br +CH3CHCH2Br BrCH2=CH2 + H OSO2OHCH3-CH2-OSO2OHH2OCH3CH2OH + H2SO4浓硫酸氢乙酯

8、稀(酸式硫酸酯)( )( )CH3-CH=CH2 + H2SO4（浓）CH3-CH-OSO2OHCH3( )CH2=CCH3CH3+ H2SO4(浓)CH3-C-OSO2OHCH3CH3( )溶于硫酸OSO2OH浓H2SO4不溶于硫酸CH2=CH2 + HO ClCl-CH2-CH2-OH-氯乙醇CH2=CH2 CH2CH2Cl+Cl2-Cl-H2O-H+CH2CH2ClClCl-CH2CH2ClOH(主)(副) -氯乙醇CHCH2Cl+CH3-CH3-CH=CH2+CHCH2CH3-ClOHCHCH2CH3-ClOHH2O-H+Cl2-Cl-2-氯-1-丙醇1-氯-2-丙醇abC=C+ H3

9、O+CH-CCH-COH2+H+H2OCH-COH-H+H+CH2=CH2 + H2OH3PO4/硅藻土300 C,78MPa。CH3-CH2-OH195 C,2MPa。异丙醇CH2=CHCH3 + H2OH3PO4/硅藻土CH3-CH-CH3OHCH CH + H2OHgSO4,稀H2SO4HC CHHOH重排 H-C-CH3O98-105 C。烯醇式酮式RC CH + H2OR-C-CH3OHgSO4,稀H2SO4RC CHHOH重排 更稳定！991H C C HHHOH C C HHOH总键能2678KJ/mol2741KJ/mol酮式烯醇式， 即为一种典型的互变异构。6R-CH=CH2

10、 + B2H62(R-CH2CH2)3BH2O2NaOH6RCH2CH2OH一烷基硼R-CH=CH2 + H BH2RCH2CH2BH2CH2=CH-R空间效应RCH2CH2OH + B(OH)3三烷基硼二烷基硼(RCH2CH2)2BHCH2=CH-R(RCH2CH2)3BH2O2,OH-H2O2的NaOH水溶液一级醇RCH=CH2RCH2CH2OHB2H6H2O2/OH-CH3(CH2)7CH=CH2CH3(CH2)7CH2CH2OHB2H6H2O2/OH-(反马),醚,醚B2H6H2O2/OH-CH3HOH HHOHHCH3+CH3(顺加)C=C(CH3)3CHHC(CH3)3B2H6H2O2/OH-(CH3)3CCH2-CHC(CH3)3OH,醚(不重排)CH3CH2CH2CH=CH2CH3CH2CH2CHCH2OHHgOAc(羟汞化)Hg(OAc)2 , H2O四氢呋喃