第12E-醛酮的制备

醛酮的制备烯烃炔烃芳烃醇醛酮羧酸羧酸衍生物1氧化2频哪醇重排氧化取代还原1氧化2卤化-水解3傅氏酰基化4加特曼-科赫反应1氧化2直接醛基化1水合2硼氢化-氧化乙醛和丙酮的工业制备一制备概貌1.醇的氧化和脱氢RCH2OHCrO3，吡啶RCHORCHOHR1CrO3，吡啶或k2Cr2O7，H+R1RO2.芳烃的氧化CH3MnO2，65%H2SO4CHOArCH3CrO3，（CH3CO)2OArCH(OCOCH3)2H2OArCHOCH3BrCrO3，（CH3CO)2OHOAc,H2SO4CH(OCOCH3)2BrH2OCHOBr例：3.Friedel-Crafts反应CH3+ClCOC6H5AlCl3COC6H5CH390%+OOOCOCOHOCH2COHOH2SO4CO91%4.盖特曼–考赫（Gattermann-Koch）反应在催化剂作用下，芳烃和HCl、CO混合物作用。ArH+CO+HClAlCl3ArCHOAlCl3,Cu2Cl2浓HClZn(Hg)+CO+HClCu2Cl2AlCl3CHO例：CH3+CO+HClCu2Cl2AlCl3CHOCH35.由炔烃(炔烃的水合)及偕二卤代物制备CHCH+H2OCH3CHORCCH+H2ORCCH3OHgSO4H2SO4HgSO4H2SO4注意：芳环上有烃基、烷氧基，则醛基主要在对位。芳环上有羟基，反应效果不好。芳环上有吸电子基团，则反应不发生。RCCH1.BH32.H2O2,OH-RCH2CHOArCH32Cl2hvArCHCl2H2OArCHO6.由烯烃制备RCHCHR11.O32.Zn,H2ORCHO+R1CHOR2CCR2'1.O32.Zn,H2O1.O32.Zn,H2OR2COR2'CO+O3CH2Cl2ZnHOAcCHO+CH2O7.酰卤的还原RCClOPd－BaSO4，H2RCHOR：烷基或芳基（罗森孟法）Rosenmund还原例：C6H5COClC6H5CHOCOClOCH3CH3LiAlH[OC(CH3)3]3CHOOCH3CH3三叔丁氧基氢化铝锂SPd－BaSO4，H2H2NCNH28.由酰卤与有机金属化合物制备C6H5COCl(C2H5)2Cd+OC6H5CC2H5C6H5COCl+R2CuLiC6H5COR练习：CH2CH2以为原料合成CH3CH2CH2CHCCH2CH3CHOCH2CH2+HClCH3CH2ClMg干乙醚CH3CH2MgCl干乙醚CH2CH2OH3O+1.2.CH3CH2CH2CH2OH解：OCH2CH2CH2CH稀NaOH△CH3CH2CH2CHCCH2CH3CHO练习：以丙酮为原料合成OCCH3CH3CH3CCH3和CCH3CH3CH3COOHOCCH3CH32CCH3OHCH3CCH3CH3OHOCCH3CH3CH3CCH3CCH3CH3CH3COONaCCH3CH3CH3COOHCH2Cl2CrO3(C5H5N)2△Cl2,NaOHH+解：1.Mg,C6H62.H3OH2SO4H2O9由羧酸制备ArCOOHR’LiArC-OLiOR’LiOLiAr-C-OLiRH2O-H2OArC-ROArCOOH+R’MgXArCOOMgX+R’HOHAr-C-OHRArCNArCNH2O-H2O-C10H7MgBrnArCC10H7-NMgBrH2OArCC10H7-NHnH2OH+ArCC10H7-OnHClArC=NHClArC=NHOHPCl5SnCl2ArCH=NHH2OArCH=O10由酰胺和腈制备11Vilsmeler-Haack合成法electrophiliciminiumcationelectrophilicaromaticsubstitution醛酮制备实例CH3CH=NHCH3CNCH3CHO*1SnCl2/HClH2O*2*3*4COOH+2CH3LiCCH3OH2O无水醚R'CCl+RCH=CH2OLewis酸R'CH-CH2CR'ClONa2CO3/H2OR'CH=CHCR'OOH-H2OH+KMnO4HOC(CH2)4COHOOSOCl2(n-C4H9)2CuLin-C4H9C(CH2)4CC4H9-nOOOOOC2H5OHOOOC2H5OHSOCl2ClC(CH2)2COC2H5OO[(CH3)2CHCH2CH2]2Cd无水乙醚(CH3)2CHCH2CH2C(CH2)2COC2H5OO*5