環(huán)境--第四章炔烴和二烯烴

1、多巴胺神經(jīng)元受損多巴胺神經(jīng)元受損Selegiline ( (司來吉蘭司來吉蘭) )叁鍵炔烴復(fù)習(xí)：烯烴親電加成反應(yīng)小結(jié)復(fù)習(xí)：烯烴親電加成反應(yīng)小結(jié)CH CH2RHXH OSO3HHHHORHRCOOHCHCH3RXCHCH3ROSO3HCHCH3RORCHCH3ROCORCHCH3ROHH2O CHCH2RXXCHCH2ROHX H2OX2X2 H2OCHCH2RO烯烴的氧化烯烴的氧化CCRRRHCORROCROH+CCRRRHOHOHCORROCRH+CCRRRHOKMnO4(濃濃，熱熱), OHK2Cr2O7, H或或(1) O3(2) H2O, ZnKMnO4(稀稀，冷冷), OH或或(1)

2、 OsO4, (2) H2ORCOOH（過過氧氧酸酸）O第四章第四章 炔烴和二烯烴炔烴和二烯烴炔烴的結(jié)構(gòu)、通式和命名炔烴的結(jié)構(gòu)、通式和命名炔烴的化學(xué)性質(zhì)炔烴的化學(xué)性質(zhì)共軛二烯共軛二烯一、炔烴的結(jié)構(gòu)、通式和命名一、炔烴的結(jié)構(gòu)、通式和命名CCRRCCRRCCHR一、炔烴的結(jié)構(gòu)、通式和命名一、炔烴的結(jié)構(gòu)、通式和命名v 系統(tǒng)命名法系統(tǒng)命名法一、炔烴的結(jié)構(gòu)、通式和命名一、炔烴的結(jié)構(gòu)、通式和命名H2CCHCH2CH2CHCHCH2CCHCH2CHCH2CCH12345678912345678912345HCH3CH21 1,5 ,5壬二烯壬二烯8 8炔炔例：二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCHCH2

3、R 炔丙位活潑炔丙位活潑 可鹵代可鹵代 鍵鍵可被氧化可被氧化末端氫有弱酸性末端氫有弱酸性可與強堿反應(yīng)可與強堿反應(yīng)二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)1 1、叁鍵上的親電加成反應(yīng)、叁鍵上的親電加成反應(yīng)烯基正碳離子烯基正碳離子不太穩(wěn)定，較難生成，不太穩(wěn)定，較難生成，一般叁鍵的親電加成一般叁鍵的親電加成比雙鍵慢。比雙鍵慢。CCHRENuCCHRECCHRorENuCCHRENu二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCHRHXCCH2RXCCH3RXXHXCCHH2CCHHClCuClCCH2H2CCHCl二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCHRROORCCRHHBrCCRBrHBrHHROORH

4、BrHBrCCRBrBrHHCCRHBrBrHorCCRHHBrBrHBr二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCHRCCRXCCRXXXHXXHXXXXCCHRZnCCHH2CCHCCHH2CCHBrBrBrBr二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCHRH2O, HgSO4CCH2RHOCCH3ROH2SO4H2O, HgSO4H2SO4CCHH2CCHCCH3H2CCHO甲基酮甲基酮二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCRRPd, Pt or NiCH2CH2RR2 H2CCRRPd / PbO, CaCO3H2CCRRHHH2Ni2B例：例：m meso-2.3-eso-2.3-丁二

5、醇丁二醇二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)合成分析合成分析（稀，冷）合成路線合成路線（稀，冷）方法方法 a a方法方法 b bCCRRKMnO4OHH+CR+O3H2OCCRHKMnO4OHH+O3H2O+OCO2OHCROOHCROOHCROHOCHOHO二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)HCCH2CuClNH4ClCCHH2CCHHCCH3(Ph3P)2Ni(CO)21.5 MPa, 6070oCHCCH41.52.0 MPa, 505oCNi(CN)2二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCRNa或或CCRMgX

6、LR( L = X, OTs)( R: 1o烷烷基基)CCRR(1)OR(2)H2OCCRCH2CHOHR(1)CROR(H)(2)H2OCCRCOHRR(H)+L CCCOHCH3CH3COHCH3CH3CCHHCCCOHCH3CH3COHCH3CH3CCCOCH3CH3COCH3CH3+CCHHCOH3CH32NaNH22CCNaNaH2OTM提示：提示：注意與注意與Na / NHNa / NH3 3 還原體系區(qū)別還原體系區(qū)別二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCHHHOHOCCHCOH3CCH3+醇醇脫脫水水二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCH

7、HNaNH2CHCNaH3CCH3HOH2Lindlar催催化化劑劑H3CCH2CH3HOAl2O3（醇醇脫脫水水試試劑劑）COH3CCH31.2. H2O二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)CCHHNaNH2CHCNaCH2CH3BrCHCCH3CH2CCH3CH2CNaNH2NaOCH2CH2OHCCCH3CH2H2Lindlar催化劑CH2CH2OHCCCH3CH2HH1.2. H2O催化劑CCRHCCRAg(NH3)2+ / OHAgCCRCuCu(NH3)2+ / OH二、炔烴的化學(xué)性質(zhì)二、炔烴的化學(xué)性質(zhì)三、共振論三、共振論CHCH2H2C14CHCH2H2C14CHCH2CH2 1

8、4三、共振論三、共振論三、共振論三、共振論CHCH2H2C14CHCH2H2C14三、共振論三、共振論共振論對共振論對共振式的畫法的一些規(guī)定共振式的畫法的一些規(guī)定CHCH2H2CCHCH2H2CCHCH2H2CCHCH2CH3H2CCHCH2CH3H2CCHCH2CH3H2CCHCH2CH3H2CCH2CHCH3H2C四、共軛效應(yīng)四、共軛效應(yīng)1 1、誘導(dǎo)效應(yīng)、誘導(dǎo)效應(yīng)CHRCH2RR誘導(dǎo)效應(yīng)隨著碳鏈的增長逐漸減弱誘導(dǎo)效應(yīng)隨著碳鏈的增長逐漸減弱！2 2、共軛效應(yīng)、共軛效應(yīng)四、共軛效應(yīng)四、共軛效應(yīng)CHCHHH2CH pCHHH pCHRORCHRORCHXRCHXRpppp四、共軛效應(yīng)四、共軛效應(yīng)

9、CCH p共軛效應(yīng)共軛效應(yīng)不會不會隨著碳鏈的增長而逐漸減弱隨著碳鏈的增長而逐漸減弱五、共軛二烯（共軛雙烯）五、共軛二烯（共軛雙烯）CCCnCHCHH2CCH2H2CCCHCH3CCHH2CCH2CH3五、共軛二烯（共軛雙烯）五、共軛二烯（共軛雙烯）GW+GWGGGORRNHRWCCO2R(H)CNNO2R(H)O有利因素有利因素:五、共軛二烯（共軛雙烯）五、共軛二烯（共軛雙烯）GW+GWGGGWG 五、共軛二烯（共軛雙烯）五、共軛二烯（共軛雙烯）OOOOOO20oCH+OOO100oC35oCCHOOO100oCOO+ 五、共軛二烯（共軛雙烯）五、共軛二烯（共軛雙烯）OOOOOO+OO+OOCO2CH3CO2CH3CO2CH3H3CO2C+五、共軛二烯（共軛雙烯）五、共軛二烯（共軛雙烯）CO2CH3HHOHOCO2CH3HHOHOCO2CH3H+CO2CH3+CO2CH3CO2CH3HCO2CH3HHOHO1. OsO4 2. H2O五、共軛二烯（共軛雙烯）五、共軛二烯（共軛雙烯）ENuCHCHH2CCH2CHCHH2CCH2123CHCHH2CCH2CHCHH2CCH2CHCHH2CCH245NuENuEENu1 1,4 ,4加成加成1 1, 2, 2加成加成CHCHH2CCH2BrHCHCHH2CCH2HBrCHCHH2