炔烴與二烯烴

1、 炔烴的結(jié)構(gòu)、命名、異構(gòu)和制備方法炔烴的結(jié)構(gòu)、命名、異構(gòu)和制備方法 炔烴的親電加成（加成類型，加成取向），在合成中炔烴的親電加成（加成類型，加成取向），在合成中 的應(yīng)用的應(yīng)用 炔烴的兩種還原方法及在合成中的應(yīng)用（順、反烯烴炔烴的兩種還原方法及在合成中的應(yīng)用（順、反烯烴 的制備）的制備） 炔烴的氧化炔烴的氧化 末端炔烴的特殊性質(zhì)及在合成中的應(yīng)用末端炔烴的特殊性質(zhì)及在合成中的應(yīng)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 炔丙位活潑炔丙位活潑 可鹵代可鹵代 p p鍵可被氧化鍵可被氧化末端氫有弱酸性末端氫有弱酸性可與強(qiáng)堿反應(yīng)可與強(qiáng)堿反應(yīng)烯基正碳離子烯基正碳離子不太穩(wěn)定，較難生不太穩(wěn)定，較難生成，一般叁鍵的親成，一般叁鍵的親電加成比雙鍵慢。電加成比雙鍵慢。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催化劑or P-2催化劑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共軛堿共軛堿化合物化合物pKa共軛堿共軛堿(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 共軛雙烯的穩(wěn)定性，與親電試劑的共軛雙烯的穩(wěn)定性，與親電試劑的1, 4加成及加成及1,2加加 成。熱力學(xué)控制與動力學(xué)控制的反應(yīng)成。熱力學(xué)控制與動力學(xué)控制的反應(yīng) DielsAlder反應(yīng)，協(xié)同反應(yīng)機(jī)理反應(yīng)，協(xié)同反應(yīng)機(jī)理 Diels

7、Alder反應(yīng)在有機(jī)合成中的應(yīng)用反應(yīng)在有機(jī)合成中的應(yīng)用CCCnCHCHH2CCH2H2CCCHCH3CCHH2CCH2CH3CHCHH2CCH2CHCHH2CCHCH3CH3CHCH2CH2CHH3CCH2CHCH2H2CCHCH2CCCHCHHHHHBrOHOHH- -HBr- -H2OstransscisCHCHH2CCH2BrHCHCHH2CCH2HBrCHCHH2CCH2HBr（無無過過氧氧化化物物）+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構(gòu)象構(gòu)象OOOOOO20oCH+OOO100oC35oCCHOOO100oCOO+ OOOOOO+OO+OOCO2CH3CO2CH3CO2CH3H3CO2C+CO2CH3HHOHOCO2CH3HHOHOCO2CH3H+CO2CH3+CO2CH3CO2CH3HCO2CH3HHOHO1. OsO4 2. H2O氧化CHOCHOCOOHCOOH123456123456orHOOCCOOH126345126345+ H2CCH2126534HOOCCOOH+H2CCH2加壓KMnO4HOOCCOOH RR+COORRRRCOORR CO2C2H5CO2C2H5OHOOCHOOCCOOHCOOHHHHOOCCOOHCOOHHO