1、 烯烴：由于鍵鍵能小，易破裂，烯烴的反響都是圍繞著鍵 進展的： 鍵電子云流動， 較松散，可作為一電子源，起lewis堿的作用，與親電試劑發生加成反響： C=C+ X-YCCXY炔烴：官能團 CC 1個、2個 有鍵：性質類似烯烴，如加成、氧化、聚合； 2個相互的：有不同于烯烴的性質，如炔氫的酸性。 H，受C=C影響，可發生取代反響。催化加氫 CH2=CH2 + H2CH3-CH3催化劑RCH2CH3Ni or Pd,PtRC CH + H2H2CH2=CH2H-CH2-CH2-HHHHHC2H4吸附解吸在適當的催化劑作用下，烯烴或炔烴與氫加成生成烷烴： Ni須經處置，得Raney Ni，又叫活性

2、Ni、骨架Ni。這種鎳特點是具有很大的外表積，便于反響按以下機理進展：中間構成一個Ni-H鍵(半氫化態)為過渡態。Cat.：Pt、Pd、Rh、Ni等。RCH=CH2RC CH + H2lindlarHC C-C CHCH2CH2OHCH3+ H2lindlarH2C CH-C CHCH2CH2OHCH3CH3CH3+ H2NiCH3H3CHHCH3CH2-C C-CH2CH3 + H2C=CCH3CH2HCH2CH3HP-2催化劑C=CHCH3CH2(CH2)3CH3HNa-液NH3-33 C。CH3CH2-C C(CH2)3CH3CH3CH2-C C-CH2CH3B2H6，醚0 C。CH3C

3、OOHC=CCH3CH2HCH2CH3H-RCHCHR-RCHCHRC=C+ Br2紅棕色無色CCl4CCBr BrRC CHRCCl=CHClRCCl2CHCl2Cl2(or Br2)Cl2(or Br2)(RCBr2CHBr2)CH2=CH-CH2-C CH + Br2CH2BrCHBrCH2C CH乙醚低溫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(常用溶劑)H-C C-HCl ClCl ClCH=CHClClCH C

4、HCl2,FeCl3,CCl480-85 C。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-角張力更大，內能更高CCBrBrCCBr+烯烴慢+ 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)21.02.035.5310.40.04C

5、H2=CHBr烷基取代增多，雙鍵上電子云密度增大，親電加成反應速率增大雙鍵上電子云密度減小，親電加成反應速率減小-Br是吸電子基!CH3-是給電子基!H2O,NaClCH2-CH2 + CH2-CH2 + CH2-CH2BrOHBrBrBrClCH2=CH2+ Br2(少量)CH2=CH2CH2CH2BrBrBr慢快Br -CH2CH2BrBrOH-Br-Cl-BrCH2CH2OHBrCH2CH2BrBrCH2CH2ClCH2 CH2Br+無無ClCH2CH2Cl !BrHBrH+ Br2CCl40 C。+BrBrHHCCBrBrCCBr+烯烴慢+ BrBrC=CBr-快+ H XC=C：(H

6、X=HCl,HBr,HI)CCHXXXHXHXR-C=CH2R-C-CH3XRC CH CH3XHCH3HXH2C=CHCl氯乙烯HClH3C-CHCl2Cu2Cl2or HgSO4HgCl21,1-二氯乙烷（有機溶劑）CH CH + HClHgCl2CH3-CH=CH2 + HBrCH3CH2CH2Br主要產物次要產物CH3-CH-CH3Br+C=CHX+X-HCC+X-HXCCHCC+馬氏規那么烯、炔加鹵化氫時，氫原子總是加到含氫 多的不飽和碳上。例如：2-氯丙烷1-氯丙烷CH3-CH=CH2 + HClCH3CH2CH2Cl主要產物次要產物CH3-CH-CH3Cl+CH3CH2CH=CH

7、2 + 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(主要產物)(次要產物)CH3-C+H-CH3CH3CH2CH2+Br-Br-CH3-CH-CH3Br()()C空p軌道+鍵 分散程度小中心C上正電荷CH3CH2HHC+穩定不如C空p軌道+( )I IC+I( )中心C上正電荷分散程度大H3CH3CHC+穩定比C空p軌道+I( )C+( )I I C的中心碳原子為sp2雜化，平面構型，有一個

8、垂直于平面的p軌道是空的： 由于C()較穩定，途徑的活化能較低，途徑的活化能較高。 丙烯與溴化氫的加成產物以為主。 CH3CH3C+H3C+HCH3CH3C+CH3C+H2CH3C+H33。C+2。C+1。C+ 留意以下C的穩定性： CH2=CCH3CH3+H+CH3-C+-CH3CH3C+H2-CHCH3CH3CH3-C-CH3CH3BrCH2-CHCH3CH3BrBr-Br-(主)(次)Cl說明烯烴加HX的反應確實經過碳正離子中間體!CH3-C-CH=CH2CH3HHCH3CH3-C-CH-CH3+HCH3CH3-C-CH-CH3ClHCl-Cl-Cl-2 碳正離子。1,2-氫遷移(重排)

9、預期產物重排產物 (主)(次)HCH3CH3-C CH-CH3CH3CH3-C-CH-CH3+H。3 碳正離子Cl-CH3-CH=CH2 + HBrCH3-CH-CH3Br（主）CH3-CH=CH2 + HBrhor 過氧化物CH3CH2CH2Br （反馬）只能是HBr (HCl、HI都不反馬) 引發R-O-O-Rh2RO過氧鍵+ CH3CH=CH2BrROROH + BrCH3-CH-CH2Br。1 ,不穩定。2 ,穩定CH3-CH-CH2BrCH3-CH-CH2Br + HBrCH3CH2CH2Br + Br增長+ H Br終止Br+BrBr2BrCH3CHCH2Br +CH3CHCH2B

10、r BrCHsp2雜化H成單電子的獲取電傾向子緩解程度大成單電子的獲取電傾向子緩解程度小CH3CHBrCCH2BrHCH3sp2雜化中心C上電子云密度比 大()中心C上電子云密度比 ()小穩定性大于穩定性小于sp2雜化未成對電子，具有強烈的獲取電子的傾向CCH2=CH2 + H OSO2OHCH3-CH2-OSO2OHH2OCH3CH2OH + H2SO4濃硫酸氫乙酯稀(酸式硫酸酯)( )( )CH3-CH=CH2 + H2SO4（濃）CH3-CH-OSO2OHCH3( )CH2=CCH3CH3+ H2SO4(濃)CH3-C-OSO2OHCH3CH3( )CH2=CCH3CH3H+CH3-C+

11、CH3CH33 C。穩定+CH2=CH-CH3CH3-C+H-CH32 CH+。+溶于硫酸OSO2OH濃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+ H3O+CH-CCH-COH2+H+H2OCH-COH-H+H+CH2=CH2 + H2OH3PO4/硅藻土30

12、0 C,78MPa。CH3-CH2-OH195 C,2MPa。異丙醇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 更穩定！991H C C HHHOH C C HHOH總鍵能2678KJ/mol2741KJ/mol酮式烯醇式， 即為一種典型的互變異構。6R-CH=CH2 + B2H62(R-CH2CH2)3BH2O2NaOH6RCH2CH2OH一烷基硼R-CH=CH2 + H

13、 BH2RCH2CH2BH2CH2=CH-R空間效應RCH2CH2OH + B(OH)3三烷基硼二烷基硼(RCH2CH2)2BHCH2=CH-R(RCH2CH2)3BH2O2,OH-H2O2的NaOH水溶液一級醇RCH=CH2RCH2CH2OHB2H6H2O2/OH-CH3(CH2)7CH=CH2CH3(CH2)7CH2CH2OHB2H6H2O2/OH-(反馬),醚,醚B2H6H2O2/OH-CH3HOH HHOHHCH3+CH3(順加)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 順-3-己烯順加!CH3(CH2)5CH=CH-BCHCH(CH3)22CH3H2O2,H2ONaOHCH3(CH2)5CH2CHO辛醛 (70%)CH3(CH2)5CH=CHOH烯醇式重排反馬CH3(CH2)5C CH(CH3)2CHCH2BHCH3+0-10 C。二甘醇二甲醚CH3C