高四3章_不飽和烴-2

1、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(dāng)?shù)拇呋瘎┳饔孟?，烯烴或炔烴與氫加成生成烷烴：Ni須經(jīng)處理，得Raney Ni，又叫活性Ni、骨架Ni。這種鎳特點(diǎn)是具有很大的表面積，便于反應(yīng)按下列機(jī)理進(jìn)行：中間形成一個(gè)Ni-H鍵(半氫化態(tài))為過(guò)渡態(tài)。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紅棕色無(wú)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 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-角張力更大，內(nèi)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)21.02.035.5310.40.04CH2=CHBr烷基取代增多，雙鍵上電子云密度增

4、大，親電加成反應(yīng)速率增大雙鍵上電子云密度減小，親電加成反應(yīng)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)+ 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（有機(jī)溶劑）CH CH + HClHgCl2CH3-CH=CH2 + HBrCH3CH2CH2Br主要產(chǎn)物次要產(chǎn)物CH3-CH-CH3Br+

5、C=CHX+X-HCC+X-HXCCHCC+馬氏規(guī)則烯、炔加鹵化氫時(shí)，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(chǎn)物次要產(chǎn)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(主要產(chǎn)物)(次要產(chǎn)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說(shuō)明烯烴加HX的反應(yīng)確實(shí)經(jīng)過(guò)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)預(yù)期產(chǎn)物重排產(chǎn)物 (主)(次)HCH3CH3-C CH-CH3CH3CH3-C-CH-CH3+H。3 碳正離子Cl-CH3

7、-CH=CH2 + HBrCH3-CH-CH3Br（主）CH3-CH=CH2 + HBrhor 過(guò)氧化物CH3CH2CH2Br （反馬）只能是HBr (HCl、HI都不反馬) 引發(fā)R-O-O-Rh2RO過(guò)氧鍵+ CH3CH=CH2BrROROH + BrCH3-CH-CH2Br。1 ,不穩(wěn)定。2 ,穩(wěn)定CH3-CH-CH2BrCH3-CH-CH2Br + HBrCH3CH2CH2Br + Br增長(zhǎng)+ H Br終止Br+BrBr2BrCH3CHCH2Br +CH3CHCH2Br BrCH2=CH2 + H OSO2OHCH3-CH2-OSO2OHH2OCH3CH2OH + H2SO4濃硫酸氫乙酯

8、稀(酸式硫酸酯)( )( )CH3-CH=CH2 + H2SO4（濃）CH3-CH-OSO2OHCH3( )CH2=CCH3CH3+ H2SO4(濃)CH3-C-OSO2OHCH3CH3( )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+ 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。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(wěn)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(gòu)。6R-CH=CH2

10、 + B2H62(R-CH2CH2)3BH2O2NaOH6RCH2CH2OH一烷基硼R-CH=CH2 + H BH2RCH2CH2BH2CH2=CH-R空間效應(yīng)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(jí)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)CH3CH2CH2CH=CH2CH3CH2CH2CHCH2OHHgOAc(羥汞化)Hg(OAc)2 , H2O四氫呋喃