1、主要内容：主要内容：醛酮的化学性质（醛酮的化学性质（）醛酮的还原反应醛酮的还原反应 醛酮的氧化反应醛酮的氧化反应 Cannizzaro反应和卤仿反应反应和卤仿反应COCHOHCOCH2HH1.LiAlH4CHROHR(H)CROR(H)or NaBH42.H2O1.B2H6/THF2.H2OCOHCOHBH2OCOHHH3BO3BH2(0.3MPa)PtCROR(H)CHROHR(H)NOH3CNiH2NOHH3CHNOHH3CH机理（了解）机理（了解）(i-PrO)3AlCH3CHOHCH3(过过量量)CROR(H)CHROHR(H)RCROAlORCROAlOCHRCROAlOCH RCR
2、OAlOCHH3CCH3 HOCH(CH3)2RCHROH AlO CH(CH3)2CH3CH3CH3CH3CH3CH3H六员环过渡态六员环过渡态蒸馏除去蒸馏除去交换交换Na or LiCROR(H)CHROHR(H)RCOHRRCOHRRCRO2Mg(Hg)RCROeRCROMNaRCRONaS（溶溶剂剂）RCHROHeH2ORCHRONaH自自由由基基二二聚聚RCORRCORMgRCOHRRCOHRPinacolH2ORCRO2eMg2RCORRCORMg适用于对酸适用于对酸稳定的体系稳定的体系RCR(H)ORCH2R(H)Zn(Hg)HClAr HCClROAlCl3ArCROZn(Hg
3、)HClArCH2R（Huang-Minlon modification）RCRORCH2RNH2-NH2,Na 200oCN2+适用于对碱适用于对碱稳定的体系稳定的体系NH2-NH2,NaOH(HOCH2CH2)2O,RCRORCH2RN2+RCRONH2-NH2RCRONH-NH2HRCROHN-NH2HOHOHRCRNNH HOHRCRNNHRCRNNHHRCH2RRCHRNNHOHRCHRN2OHH H2ORCR(H)ORCR(H)SSHSSHRCR(H)H2Raney NiH+HHRCOHOORCHORCHORCONH4O2 Ag(NH3)2OH+2 AgRCONaO+Cu2OCu(
4、OH)2/NaOHRCHORCOOHOO2RCOHO2RCHO产物复杂，合成应用意义不大产物复杂，合成应用意义不大R1COHOR1CH2CCH2R2OCCH2R2OHOR1CH2COOHCR2OHO强强氧氧化化剂剂+O浓浓 HNO3COOHCOOH有合成意义有合成意义Baeyer-Villiger反应反应R1CR2ORCOOHOR1COR2OR1OCR2OCOOHOH3CCOOHOF3CCOOHOCOOHO(MCPBA)ClR1CR2ORCOOHOH+R1CR2OHHOR1CR2OHO CROH+OR1CR2OHOCRO R1OR1CR2OHOCROH H+OCOHR1OCR2OHH+R1OC
5、R2O（来来自自过过氧氧酸酸）R迁迁移移碳正离子重排碳正离子重排Pinacol重排重排CRC RCCRCRCROHR OH2R RCCRORRRH2OORB OH RHOOBRROHB(OH)3H2O+RCRNRCRNOH2 RH2ORCRNHOH2O烯烃的硼氢化烯烃的硼氢化氧化反应氧化反应Beckmann重排重排CR3CHR2CH2CH2RCH3CCH3OCCH3OOOOOPhCO3HCH3CO3HOCOOOHH3CCOOEtH3COO己己内内酯酯HOCOOH(1)OH(2)H2O/H+RCH浓浓 OHORCOORCH2OH+H+RCOOH+RCHO例：例：CHO2CH2OHCOOHOHOC
6、HOOCH2OHOCOOH2OHRCOHOHRCOHOHRCOHRCOHOHRCOH+HRCOO+HRCOHH负负H迁迁移移产物复杂，一般无合成意义产物复杂，一般无合成意义R1CH浓OHOR1COOR2CH2OHR2CHO+R2COOR1CH2OH+R CH浓OHOHCOORCH2OHCH2O+R CHOHCOORCH2OHCH2O+OHCH3CHOOHCCH2OHCH2OHHOH2CCHOCH2OCCH2OHCH2OHHOH2CCH2OHOH3 CH2O羟醛缩合羟醛缩合Cannizzaro反应反应PhCCHOOOHPhCCOOHOHPhCCPhOOOHPhCCOOHOPhOHCH3COR3 X2CX3CORCHX3CORO+OHCH2CORHOCX3CORCOROHCX3COROHCOROCHX3+HOCH2CORXXCHCORXCX3HHOHCHCORXCHCORXXXX+aaH有有弱酸性弱酸性烯醇负离子烯醇负离子亲核加成亲核加成消除消除
