有机化学09-2

1、COHCHH H+COH2CHH 提示：提示：使用强碱时，使用强碱时，注意羟基的注意羟基的保护。保护。ROH+NaRONa+H2CH3OHCH3CH2OHCH3CHOHCH3CH3COHCH3CH3ROHRMgXRONaNaNH2ROMgX+NH3+RHNaHRONa+H2 Brnsted碱碱 Lewis碱碱好离去基好离去基好离去基好离去基ROHH+ROH2ROHROHZnCl2ZnCl2NuRNu+H2OClRCl +HOZnClROHRXROR+HXSN2+醚醚ROHH+ROHROHH2OH+RHORHRORSN2ROHRORH+H2OROH+醚醚ORH+OHRORROH+ORH+ORHR

2、HOOHRROHH+OHROR SN2CH2H3CH3CH+ROHH+CCH3CH3CH3OHRCCH3CH3CH3ORCCH3CH3CH3H2CCH3CH3H+ROH+ORCCH3CH3CH3RXROR+HXSN1ROH+HOBrHOCH3OHHOBrH2CCH3CH3H+OBrCCH3H3CCH3Mg无无水水乙乙醚醚OMgBrCCH3H3CCH3(1) CH3CHOOCCH3H3CCH3CH3OH(2) H2OH+H2OHOCH3OH+H2CCH3CH3ROHH+OOORH+H2OROH+OOHORTHPOCOHRH+ROH+OCORR+H2OOCOHROHCOHRROHOHCOHRROH

3、OHCOHRROHOHCORRH2OH+OCORRH+OCRRH+OHCRRORH+ROHORCRRORROH+RCROHRCRORCROHROHRCROHORRCROHORRCRORRCRORORHRCRORORHORHOROH2H+H+H+HSO2ClH3CROH+3 HCl+ROPOCl2ROH2(RO)3POSO2ORH3C+HClPOCl3ROH+HNO2H2SO4H+RONO2RONOROSO3HH2O+HNO3IHROHBrHor NaBr / H2SO4ClHZnCl2,RBrRIRClROHHROH2RXRH2ORXX(SN2)(SN1)H2O+X( X = Br, I)RO

4、HROHZnClZnCl2ClClROHZnClClRClHOZnCl(SN2)R(SN1)ClRCl+HOZnCl+Locus试剂ZnCl2/HCl：鉴别醇的级别ROH + HCl RCl + H2OZnCl2醇的比重1，观察浮在上层的醇沉入下层的时间即可判断醇的级别：phCH2OHCH2=CHCH2OH30 20 10很快 很慢，且需加热。ROH+RBrPBr3RIPI3or P, I2ROHPBrBrBrROHPBrBrBrRBr+HOPBr2(SN2)反应有两种立体选择性反应有两种立体选择性（与溶剂有关）（与溶剂有关）构型翻转构型翻转构型保持构型保持OH +SOCl2醚为溶剂SOCl2

5、NHRRClHRRClHRRSClClOOHHRROSClClOHHRROSClOHRR构型翻转构型翻转NOSClONCl SO2 N（SN2）OSClOHRRHRRCl OSONHRRHRRCl构型保持构型保持OSClOHRRCHRROSClOCHRRCl+SO2SNi机理机理（ Substitution Nucleophlic internal, 分子内取代机理）分子内取代机理）OHRTsClOTsRNaCNKOAcNaICNROAcRIR+OTsCH3SOOOHRRNuHRRNu+CH3SOOO（SN2）H3CSO2ClCH3HPhOHTsClCH3HPhOTsC2H5OKCH3HPhC

6、2H5OCH3HPhOHKCH3HPhOKC2H5OTsCH3HPhOC2H5第四章第四章 ppt：0042ROHROH2ROHZnClROHPBr2ROSONROTsNuRNuCCHOHH+CCH2O+Al2O3 CCHOHH+CCCCHOH2BE2H2O+HBH2OCCHBE1CC+HBCH3CH2CCH3OHCH3H3CCH3CH3+H3CCH3CH2CH3CH2CHCH2CH3OHH2SO4, H2OCH3COHCH3CH3CHCH3H2SO4, H2OH+H3CCCCH3CH3H3C+CH3CCHCH3CH3H2COHAl2O3OHOHAl2O3 CH2ROHCHROHRCROHRC

7、H2R O CHRO O COOHR O CROR O 碱碱性性、中中性性不不反反应应 O CRRCHR,H2OH+ O RCOOH +CRRO酸酸性性 用常见的强氧化剂用常见的强氧化剂（HNO3, KMnO4 / OH，K2Cr2O7 / H2SO4）氧化致）氧化致最终产物最终产物CH2CH2CHHOCHCH2OHCH2CH2CHHOCHCHOHOHOOHMnO2OHOOHMnO21o醇醇 羧酸羧酸HOCrO3, H2SO4丙丙酮酮OCH2ROHCOOHRCrO3, H2SO4;丙丙酮酮2o醇醇 酮酮1o 醇醇 醛醛 2o 醇醇 酮酮CrO3N2OHOCrO3NCH2OHH3C(H2C)4C

8、rO3(C5H5N)2COH3C(H2C)4HCH2Cl21o 醇醇 醛，醛， 2o 醇醇 酮酮CHROHRCROR+CH3COCH3CHH3COHCH3+AlOC(CH3)332o醇醇 酮，酮，不影响双键不影响双键AlOC(CH3)33CHROHR+AlOC(CH3)32OCHRR+CH3COHCH3CH3AlOCRRHOCH3CCH3AlOCRRHOCH3CCH3OBu-tOBu-tOBu-tOBu-tAlOCRRHOCH3CCH3OBu-tOBu-t+：OHAlOC(CH3)33CH3COCH3OCHROHRCROR+CH3COCH3CHH3COHCH3+AlOC(CH3)33CCHOHCCHOCCHXCCHOCCCCHORCCOHHOCORCCHOTsCCHNu失失去去氢氢成成醚醚成成磺磺酸酸酯酯取取代代酯酯化化卤卤代代消消除除氧氧化化CCHOor1)2)H2COHHCCH2OHOH+3HNO3H3CSO2OHPCl5HOC(CH3)33)SO2OHPCl5CH3CHHOCH2CH2CH3NaI丙酮O2NOH2CHCCH2ONO2ONO2H3CSO2ClH3CSO2OC(CH3)3SO2ClSO2OCHCH3CH2CH2CH3CHH3CH3CH2CH2CI1)CH2OHNa2Cr2O7H2SO4,2)OH新制MnO2O