有机化学003烯烃2

1、主要内容主要内容n 邻基参与效应邻基参与效应n 烯烃的离子型聚合反应（二聚与多聚）烯烃的离子型聚合反应（二聚与多聚）n 烯烃加成的过氧化效应烯烃加成的过氧化效应自由基加成及聚合自由基加成及聚合n 烯烃的催化氢化及立体化学烯烃的催化氢化及立体化学n 烯烃的氧化，氧化反应在合成上的应用烯烃的氧化，氧化反应在合成上的应用HXHOSO3HHHORRCOOHCHCH3RXCHCH3ROSO3HCHCH3RORCHCH3ROCORCHCH3ROHCHCH2RXXCHCH2ROHX H2OX2 orX2 H2OHH orCCHHHRENuCCRHHHENuCCHHHRENu CCXXCCXXCCXXSN2C

2、CXXCCXH2OCCXOH2CCXH2OCCXOHCCXHO H HBr2 / CCl4BrHHBrBrHHBr+BrBr BrBrBrBrBrBr HHBrBrBrBrBrBrHH 向上向上向上向上向向下下向上向上CH3CH3BrBrCH3CH3HHBrBrabCH3CH3HHBrBrCH3BrHCH3HBraCH3CH3HHBrBrbCH3BrHCH3HBrCH3CH3CH3BrHCH3HBrCH3BrHCH3HBr+H3CCH3Br2CH3BrHCH3HBrBr2注意立体表达式注意立体表达式之间的转换之间的转换硼氢化反应硼氢化反应 v也有人认为，硼氢化反应的方向由立体因素决定，也有人认

3、为，硼氢化反应的方向由立体因素决定，与不对称的烯烃加成时，硼原子主要加在位阻小的双与不对称的烯烃加成时，硼原子主要加在位阻小的双键碳上。键碳上。 +(BH3)212RCH2CH2BH2RCH CH2v电负性：氢电负性：氢2.1，硼，硼2.0，按马氏规则硼原子加在含氢，按马氏规则硼原子加在含氢较多的双键碳上。较多的双键碳上。 v硼氢化反应分三步进行，生成三烷基硼。硼氢化反应分三步进行，生成三烷基硼。 +(BH3)212RCH CH2RCH2CH2BH2RCH CH2(RCH2CH2)2BHRCH CH2(RCH2CH2)3Bv生成的三烷基硼，用碱性过氧化氢氧化后生成醇。生成的三烷基硼，用碱性过氧

4、化氢氧化后生成醇。3H2O2+3RCH2CH2OHB(OH)3+(RCH2CH2)3BOH(1) (BH3)2CH3 CH CH2OHCH3CH3 C CH2CH3(2) H2O2 , OH3 NaBH4+ 4 BF32 B2H6+ 3 NaBF4v烯烃的硼氢化烯烃的硼氢化- -氧化反应，相当于烯烃和水的反马氧化反应，相当于烯烃和水的反马氏规则的加成反应。氏规则的加成反应。 v二硼烷在空气中会自燃，因此，是在反应时现场制二硼烷在空气中会自燃，因此，是在反应时现场制取，使生成的取，使生成的B2H6立即与烯烃反应。立即与烯烃反应。 R*OHHBrR*OH2BrR*Br+H2OR*OHHBrR*OH

5、2BrRBr H2OR( )CCBrOHHBrCCBrBrR*OHHBrR*BrCH3HBrCH3HOHorCH3HBrCH3HHOHBrCH3HBrCH3HBrCH3HBrCH3HHOorCH3HBrCH3HOHHBrCH3HBrCH3HBrCH3HBrCH3HBr手性碳手性碳构型保持构型保持50构型构型全全保持保持50构型构型全全翻转翻转CH3HBrCH3HOHHBrCH3HBrCH3HOH2HH3COH2HCH3BrHH3CHCH3BrBrababHH3CHCH3BrBrHH3CHCH3BrBrCH3HBrCH3HBrCHCH2ClHClCHCH3ClCl+CHCH2ClHClCCH3C

6、lHCHCH2ClorCHCH2ClHHCHCH2ClHClCCROCCR2NH2OCCROCCR2NHOHHOHH2OHHCCROHHO+CCR2NHHO+HHOROHH+OOROCCHRCCHRH CCRCCHHCCHHCCH2CH3H3C260% H2SO4100oC或或 H3PO4,CCH2CH3CH2CCH3H3CCH3CCH3CH3CHCCH3H3CCH3+80%20%CCH2CH3H3CCCH2CH3CH2CCH3H3CCH3CCH3CH3CHCCH3H3CCH3HCCH3CH3H3CCH2CCH3CH3CCH2CH3CHCCH3H3CCH3HHOSO3HabbaCCH2H3CC

7、H2CCH3H3CCH3HOSO3H CCH3CH3CCCH3H3CH3CHHO3SO OSO3HH3CCH3CH3CH3HH3CCH3CH3CH3CH3H3CH3CH3CCH3H3CH3CH3CHCH3H3CH3CH3CH H3CCH3CH3CH3HCH3H3CH3CH3COHOO CCH2RRnCCH2RRnBF3BF3+ H2OHBF3OH+CCH2RRHCCH3RRCH2CRRCH3CRRCCH2RRCCH2RRnCH2CRRCCH2CH3H3CHBrCCH2CH3H3CHBrCCH2CH3H3CBrH过氧化效应过氧化效应ROOROROORRO2ROHBrROH+BrBrCCH2CH3

8、H3C+CCH2CH3H3CBrCCH2CH3H3CBrHBr+CCH2CH3H3CHBr+Br CCH2PhHnCCH2PhHnPhCO OCPhOO PhCO OCPhOO PhCOO2CH2CPhH2BzOBzOCCH2PhHBzOCH2CPhHCCH2PhHBzOCCH2PhHCH2CPhHCCH2PhHnCC+催催化化剂剂CCHHH2（ Ni(Al) + NaOHNi + NaAlO2 + H2 ）骨骨架架镍镍HHHHHHCCCCHCCHHCCH+ H 120kJ/molCCH2+CHCHCH3CH3+H2Pt,CH3CH3CH3CH370-8515-30CH3CH2CH3CH3CH

9、3CH37030+H2PtCH2CH3位位阻阻较较大大位位阻阻较较小小H2PtCH3CH3H位阻为主要位阻为主要影响因素影响因素CH3CH3+H2PtCH3CH3HHCH3CH3+H2PtHHCH3CH3H3CCH3H3CCH3CCRRRHCORROCROH+CCRRRHOHOHCORROCRH+CCRRRHOKMnO4(浓浓，热热), OHK2Cr2O7, H或或(1) O3(2) H2O, ZnKMnO4(稀稀，冷冷), OH或或(1) OsO4, (2) H2ORCOOH（过过氧氧酸酸）OCCH2RRCCH2RHCORRCORHO+CO2 + H2OR(H)R(H)CKMnO4(浓浓，热

10、热), OHK2Cr2O7, H或或KMnO4(浓浓，热热), OHK2Cr2O7, H或或同同上上条条件件+CO2 + H2OOR(OH)CR(OH)OCORROCROH+KMnO4(浓浓，热热), OHK2Cr2O7, H或或CCRRRHCCRRRHCORROCRH+(1) O3(2) H2O, ZnCCHOOOCCHOOOCCHOOOCCHOOOH2OCOCHO+H2O2b. 有机分析上用于分析烯烃的结构有机分析上用于分析烯烃的结构CCH2RHCORHR(H)H(1) O3(2) H2O, Zn+OCH2(1) O3(2) H2O, ZnCOR(H)CHOCOH3CC2H5OCCH3H+

11、(2) H2O, ZnCH3CC2H5CCH3H(1) O3CCRRRHCCRRRHOHOHKMnO4(稀稀，冷冷), OH或或(1) OsO4, (2) H2OHOOHRRRHOHRHOHmesoKMnO4(稀稀，冷冷), OH或或(1) OsO4, (2) H2OKMnO4(稀稀，冷冷), OH或或(1) OsO4, (2) H2OKMnO4OsO4OMnOOOOOsOOOHHHHH2OHOOHHH+MnO3MnO2MnO4OsO3H2OHOOHHH+HOCCRRRHCCRRRHOORCOOHCH3CO3HPhCO3HCF3CO3HCO3HCl(MCPBA)CCCCOHOOROHORO+C

12、CHOOROH3CPhCO3HH3COH3CO+CO3HClOHH99%Na2CO3Na2CO3加成主要发生在加成主要发生在位阻小的一边位阻小的一边RRRROHHRRRROHHNa2CO3Na2CO3ORCOOHORCOOH 构型构型“保持保持”HOOHRCO3HOH2O, H()OHOHH2OSN2HOOHH2OOH()()HRRRCO3HRROH2O, HHHRHOHRHHO()KMnO4(稀稀，冷冷), OH或或(1) OsO4, (2) H2ORHOHRHOH烯丙位氯代的条件：烯丙位氯代的条件：高温（气相）、高温（气相）、Cl2低浓度低浓度CHCH2H3C+500 600oC液液相相气

13、气相相CHCH2H3CClClCHCH2H2CClCl2CCl4烯丙位烯丙位CHCH2CH2ClCl2 Cl(1)(2)Cl+HCl+(3)ClCl+HCHCH2CH2CHCH2CH2ClCHCH2CH2Cl CCCHHHHHCHCH2CH2CCH2CHHHCCCHHHHH等性等性CHCH2CH2ClCl2 Cl(1)(2)Cl+HCl+(3)ClCl+HCl 14CHCH2H2C14CHCH2H2C14CHCH2CH2 14CHCH2H2CCl14CHCH2H2C14Cl+ClH2CCHCH2Rhv or X2H2CCHCHRXH2CCHCHRX+NBSBr(PhCOO)2NBS:NOOBrNBS 持续提持续提供低浓度供低浓度 Br2NOOBr +HBrNOOH+Br2(PhCOO)22 PhCOO2 Ph+PhBr+PhBrBr+2 CO2 BrNBS