高四3章_不饱和烃-2

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1、 烯烃：由于键键能小，易破裂，烯烃的反应都是围绕着键 进行的：键电子云流动，较松散，可作为一电子源，起lewis碱的作用，与亲电试剂发生加成反应：C=C+X-YCCXY炔烃：官能团 CC 1个、2个 有键：性质类似烯烃，如加成、氧化、聚合；2个相互的：有不同于烯烃的性质，如炔氢的酸性。H，受C=C影响，可发生取代反应。(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

2、。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。RCH=CH2RC CH+H2lindlarHC C-C CHCH2CH2OHCH3+H2lindlarH2C CH-C CHCH2CH2OHCH3CH3CH3+H2NiCH3H3CHHCH3CH2-C C-CH2CH3+H2C=CCH3CH2HCH2CH3HP-2催化剂C=CHCH3CH2(CH2)3CH3HNa-液NH3-33 C。CH3CH2-C C(CH2)3CH3CH3CH2-C C-CH2CH3B2H6，醚0 C。CH3COOHC=CCH3CH2H

3、CH2CH3HC=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。Cl2,FeCl3

4、,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大，亲电加成反应速率增大

5、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)CH2=CH2CH2CH2BrBrBr慢快Br-CH2CH2BrBrOH-Br-Cl-BrCH2CH2OHBrCH2CH2BrBrCH2CH2ClCH2 CH2Br+无无ClCH2CH2Cl!BrHBrH+Br2CCl40 C。+BrBrHHCCBrBrCCBr+烯烃慢+BrBrC=CBr-快+H XC=C：(HX=HCl,HBr,HI)CCHXXXHXHXR-C=CH2R-C-CH3XRC CH

6、 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+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

7、)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-CH3Br()()C空p轨道+键 分散程度小中心C上正电荷CH3CH2HHC+稳定不如C空p轨道+()I IC+I()中心C上正电荷分散程度大H3CH3CHC+稳定比C空p轨道+I()C+()I I C的中心碳原子为sp2杂化，平面构型，有一个垂直于平面的p轨道是空的：由于C()较稳定，途径（）的活化能较低，途径（）的活化能较高。丙烯与溴化氢的加成产物以为主

8、。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-CH=CH2 +

9、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 BrCHsp2杂化H成单电子的获取电倾向子缓解程度大成单电子的获取电倾向子缓解程度小CH3CHBrCCH2BrHCH3sp2杂化中心C上电子云密度比 大()中心C

10、上电子云密度比 ()小稳定性大于稳定性小于sp2杂化未成对电子，具有强烈的获取电子的倾向CCH2=CH2+H OSO2OHCH3-CH2-OSO2OHH2OCH3CH2OH+H2SO4浓硫酸氢乙酯稀(酸式硫酸酯)()()CH3-CH=CH2+H2SO4（浓）CH3-CH-OSO2OHCH3()CH2=CCH3CH3+H2SO4(浓)CH3-C-OSO2OHCH3CH3()CH2=CCH3CH3H+CH3-C+CH3CH33 C。稳定+CH2=CH-CH3CH3-C+H-CH32 CH+。+溶于硫酸OSO2OH浓H2SO4不溶于硫酸CH2=CH2 +HO ClCl-CH2-CH2-OH-氯乙醇C

11、H2=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+H3O+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

12、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+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=

13、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)C2H5C CC2H5。B2H6,0 C二甘醇二甲醚C=CC2H5C2H5H3C=CC2H5C2H5HHC2H5CH2CC2H5OBH2O2,OH-H2O,62%CH3COOH25 C,68%。3-己酮 顺-3-己烯顺加!CH3(CH2)5CH=CH-BCH

14、CH(CH3)22CH3H2O2,H2ONaOHCH3(CH2)5CH2CHO辛醛(70%)CH3(CH2)5CH=CHOH烯醇式重排反马CH3(CH2)5C CH(CH3)2CHCH2BHCH3+0-10 C。二甘醇二甲醚CH3CH2CH2CH=CH2CH3CH2CH2CHCH2OHHgOAc(羟汞化)Hg(OAc)2,H2O四氢呋喃CH3CH2CH2CHCH3OH(脱汞)NaBH4甲氧基乙烯or甲基乙烯基醚CH CH+CH3OHCH2=CH-OCH320%KOH水溶液,P强亲核试剂CH3OH+KOHCH3OK+H2O可离解为CH3O-+K+CH CH+CH3O-HC-=CH-OCH3CH2=CH-OCH3+CH3O-CH3OH