炔烃与二烯烃

1、 炔烃的结构、命名、异构和制备方法炔烃的结构、命名、异构和制备方法 炔烃的亲电加成（加成类型，加成取向），在合成中炔烃的亲电加成（加成类型，加成取向），在合成中 的应用的应用 炔烃的两种还原方法及在合成中的应用（顺、反烯烃炔烃的两种还原方法及在合成中的应用（顺、反烯烃 的制备）的制备） 炔烃的氧化炔烃的氧化 末端炔烃的特殊性质及在合成中的应用末端炔烃的特殊性质及在合成中的应用l CCRRCCRRCCHRHCH3CH2CH2CHCH2CCH12345CaO + C1800 - 2100 oCCaC2 + COCCCa 2+H2OCCHH+ Ca(OH)2H3CCHOCCRRRCHXCRXHRCH

2、CRXNH2E2消除NH2OHorE2消除CCRRRCHCHRRCHXCRXH2 NaNH2(1) KOH(2) NaNH2CCRRRCXXCRHH2 NaNH2CCRRRCXXCRHHRCHCRXNH2E2消除NH2E2消除CCRRRCXXCRXX2 Zn or MgRCCR+2 ZnX2XXRXXRZnXRXRRRZnZnXRXXRXZnCCHCH2R 炔丙位活泼炔丙位活泼 可卤代可卤代 p p键可被氧化键可被氧化末端氢有弱酸性末端氢有弱酸性可与强碱反应可与强碱反应烯基正碳离子烯基正碳离子不太稳定，较难生不太稳定，较难生成，一般叁键的亲成，一般叁键的亲电加成比双键慢。电加成比双键慢。CCH

3、RENuCCHRECCHRorENuCCHRENuCCHRHXCCH2RXCCH3RXXHXCCHH2CCHHClCuClCCH2H2CCHClCCHRROORCCRHHBrCCRBrHBrHHROORHBrHBrCCRBrBrHHCCRHBrBrHorCCRHHBrBrHBrCCHRCCRXCCRXXXHXXHXXXXCCHRZnCCHH2CCHCCHH2CCHBrBrBrBrCCHRH2O, HgSO4CCH2RHOCCH3ROH2SO4H2O, HgSO4H2SO4CCHH2CCHCCH3H2CCHO甲基酮甲基酮CCHRHCCHCCRRCCH3HOCCH3ROCCH2ROH2O, Hg+

4、H+H2O, Hg+H+RH2O, HgSO4H2SO4CCRRPd, Pt or NiCH2CH2RR2 H2CCRRPd / PbO, CaCO3H2CCRRHHH2Ni2BCCRRCCRRHHNa or LiNH3(液)78oCNa + NH3Na+ + e(NH3)CCRReCCRRCCRReCCRRHHHCCRRHNH2HNH2NH2HNH2CCH3CCH3CH3OHHCH3OHHmeso2, 3丁二醇CH3OHHCH3OHHCH3CH3+OsO4 or KMnO4(稀、冷)H3CCH3+RCOOOH, H2OabCCH3CCH3Lindlar催化剂or P-2催化剂CH3CH3Os

5、O4 orCH3OHHCH3OHHKMnO4(稀、冷)H2Na or LiNH3(液),78oCH3CCH3(1) RCO3H(2) H2O, H+CCH3CCH3CH3OHHCH3OHHCCRRKMnO4OHH+CR+O3H2OCCRHKMnO4OHH+O3H2O+OCO2OHCROOHCROOHCROHOCHOHO化合物化合物pKa共轭碱共轭碱化合物化合物pKa共轭碱共轭碱(CH3)3C- -H71(CH3)3CHC C- -H26HC CCH3CH2- -H62CH3CH2(CH3)3C C- -H25.5(CH3)3C CCH3- -H60CH3CH3CH2O- -H16CH3CH2O

6、H2N- -H36H2NHO- -H15.7HOCCRHRMgXRONaCCRNa+CCRMgX+RHNaNH2NH3CCRHCCRAg(NH3)2+ / OHAgCCRCuCu(NH3)2+ / OHHCCH2CuClNH4ClCCHH2CCHHCCH3(Ph3P)2Ni(CO)21.5 MPa, 6070oCHCCH41.52.0 MPa, 505oCNi(CN)2 共轭双烯的稳定性，与亲电试剂的共轭双烯的稳定性，与亲电试剂的1, 4加成及加成及1,2加加 成。热力学控制与动力学控制的反应成。热力学控制与动力学控制的反应 DielsAlder反应，协同反应机理反应，协同反应机理 Diels

7、Alder反应在有机合成中的应用反应在有机合成中的应用CCCnCHCHH2CCH2H2CCCHCH3CCHH2CCH2CH3CHCHH2CCH2CHCHH2CCHCH3CH3CHCH2CH2CHH3CCH2CHCH2H2CCHCH2CCCHCHHHHHBrOHOHH- -HBr- -H2OstransscisCHCHH2CCH2BrHCHCHH2CCH2HBrCHCHH2CCH2HBr（无无过过氧氧化化物物）+CHCHH2CCH2ClCHCHH2CCH2ClCHCHH2CCH2HCl 20oC7580%75%25%2520%+HHCHCHH2CCH2ClCHCHH2CCH2ClCHCHH2CC

8、H2Cl2+ClCl 200oC67%70%30%33%CHCHCHCHHClCH3CH3CHCHCHCH CH3CH3HClCHCHCHCHClHCH3CH3+GW+GWGGGORRNHRWCCO2R(H)CNNO2R(H)O有利因素有利因素:GW+GWGGGWG s-cis构象构象OOOOOO20oCH+OOO100oC35oCCHOOO100oCOO+ OOOOOO+OO+OOCO2CH3CO2CH3CO2CH3H3CO2C+CO2CH3HHOHOCO2CH3HHOHOCO2CH3H+CO2CH3+CO2CH3CO2CH3HCO2CH3HHOHO1. OsO4 2. H2O氧化CHOCHOCOOHCOOH123456123456orHOOCCOOH126345126345+ H2CCH2126534HOOCCOOH+H2CCH2加压KMnO4HOOCCOOH RR+COORRRRCOORR CO2C2H5CO2C2H5OHOOCHOOCCOOHCOOHHHHOOCCOOHCOOHHO