高四3章-不饱和烃-3 .ppt

1、(保持双键构型!)C=CC-CO有机过酸常用的过酸有：OC6H5-C-O-O-HOCF3-C-O-O-HOH-C-O-O-HC-O-O-HClOCH3-C-O-O-HO过氧甲酸过氧乙酸过氧苯甲酸过氧间氯苯甲酸三氟过氧乙酸+m-ClC6H4CO3HO80 C。Ph-CH=CH-COOEtCH3CO3HCH3COOEtPh-CH-CH-COOEtOCH3CO3HC=CHCHC6H4Cl-pHp-ClC6H4C-COp-ClC6H4CHC6H4Cl-pHHCH3(CH2)5CH=CH2+H2O2二氯甲烷80%CHOCH2CH3(CH2)5-1,2-环氧辛烷C=C+KMnO4CCOH OH+MnO2O

2、H-,H2O顺式氧化!此反应可在实验室制备邻二醇，但产率很低。如果用浓度较大的KMnO4的酸性溶液，结果是得到双健断裂产物：R-CH=CH2RCOOH +CO2KMnO4C=CRHRRKMnO4R-C-R +RCOOHOKMnO4C=CRRHR 酸RRHRC=O +O=C醛 酮KMnO4O=CROHC=CRRHHKMnO4RRC=O+O=C酮甲醛HH碳酸CO2+H2OKMnO4O=COHOHRC CH+KMnO4RCOOH+CO2+MnO2H2O紫红+O3C=CRRHRRRHROOCOCH2ORRHRC=O +O=C醛 酮+H2O2RRHROOCOCH2O2H2O/ZnRRC=O +O=CRO

3、H（酮）（酸）RRHRC=O +O=C（醛）（酮）某烯烃O3H2O/ZnHHC=O +O=CCH3CH3HHC=O +O=CCH3CH3C=CHHCH3CH3(异丁烯)某烯烃O3H2O2/H2OHOC=O +O=C C=O +O=CCH3CH3CH3OH OH例2：HOC=O +O=C C=O+O=CCH3CH3CH3OH OHCH3CH=CH-CH=CCH3CH3 随着工业臭氧发生器的改进，烯烃臭氧化反应在工业上得到了应用。那么，原来的烯烃为：-C C-(1)O3(2)H2O-C-C-+H2O2-COOH+HOOC-OOCH3CH2CH2C CCH3(1)O3(2)H2OCH3CH2CH2C

4、OOH+HOOCCH3丁酸乙酸CH2=CH2+O212Ag250 C。CH2-CH2OCH2=CH2+O2CH3-C-H+H2O120 C。PdCl2-CuCl2OCH3CH=CH2 +O2PdCl2-CuCl2,H2O120 C。CH3CCH3OCH3-C=CH2CH3+50%H2SO4100 C。CH3-C-CH2-C=CH2CH3CH3CH3+CH3-C-CH=C-CH3CH3CH3CH3CH2=CCH3CH380%20%CH3-C-CH2-C=CH2CH3CH3CH3+CH3-C-CH=C-CH3CH3CH3CH3CH2=CCH3CH3CH3-C+CH3CH3H+CH2=C(CH3)2

5、CH3-C-CH2-C-CH3CH3CH3CH3+-H+2CH CHCuCl-NH4ClCH2=CH-C CH乙烯基乙炔CH2=CH-C C-CH=CH2CuCl-NH4ClCH CH二乙烯基乙炔高压聚乙烯n CH2=CH2CH2CH2n自由基引发剂100 C，1000MPa。(低压聚乙烯)(C2H5)3Al-TiCl4CH2-CH2nn CH2=CH2CH2-CHnCH3n CH2=CHCH3(C2H5)3Al-TiCl450 C,1MPa。（聚丙烯）n CH2=CH2+n CH=CH2CH3共聚CH2-CH2-CH-CH2CH3n乙丙橡胶HCCHCH=CHnC=CC=CC=CHHHHHHC

6、CCCCCHHHHHH顺聚乙炔反聚乙炔聚乙炔，可导电经“掺杂”导电性更高太阳能电池、电极、半导体材料研究热点CH2=CH-CH3HC(与双键相连的碳)CH2=CH-CH3+Cl2CH2=CH-CH2Cl+HCl烯丙基氯氯丙烯或500 C。Br+Br2h3-溴环己烯Cl22Cl热引发 Cl +CH2=CH-CH2-HCH2=CH-CH2+HClCH2=CH-CH2+Cl2CH2=CH-CH2Cl+Cl增长.Cl22Cl.终止CH3CH=CH2+BrCH2CH=CH2CCCN-HCH2H2OOCCCN-BrCH2H2OO+hCCl4N-溴代丁二酰亚胺(NBS 专门溴代-H)CH3(CH2)4CH2

7、CH=CH2NBSCH3(CH2)4CHCH=CH2Br+CH3(CH2)4CH=CHCH2Br3-溴-1-辛烯1-溴-2-辛烯(烯丙位重排产物)(-溴代产物)钼酸铋等CH2=CH-CH3+O2CH2=CH-CHO+H2O370 C。(ABS、丁腈橡胶单体)CH2=CH-CH3+NH3+O2磷钼酸铋470 C。CH2=CH-CN+H2O23丙烯腈(人造羊毛单体)氨氧化法R-C C H CH CH+Na CH CNa Na液NH3 C CNa Na液NH3乙炔钠乙炔二钠RC CH+NaNH2 液NH3RC CNa+NH3炔化钠RC CNa+RX R-C C-RNaC CNa+2RX R-C C-R例：CH3C CC2H5+NaBrCH3C CNa+C2H5BrCH3C CCH3+2NaICNa CNa+2CH3ICH CH+2Ag(NH3)2NO3乙炔银(灰白色)AgC CAg +NH4NO3+NH3CH CH+2Cu(NH3)2ClCuC CCu +NH4NO3+NH3乙炔铜(砖红色 )RC CHAg(NH3)2NO3Cu(NH3)2ClRC CAg 炔银（灰白）RC CCu 炔铜（砖红）RCCHRCCRAg(NH3)2NO3RCCAgx(灰白)例：