十章节醛和酮2ppt课件

1、RCH(R)OHR2. H2O1. RMgXRC(R)HOHCCRMCCRRCH(R)OHHLiAlH4or NaBH4RCH(R)ORCH(R)OHCNHCN / NaOHRCSO3HONaH(R)NaHSO31.1.2. H2O2. H2OCOCONuHNuH OHORHHHNHRNR2HNuH可逆可逆结论：结论：分子型亲分子型亲核试剂难直核试剂难直接与羰基加接与羰基加成成COH+COHHNuCOHNuHHHCOHNuCOHNuCOHOHCOHORCOHNHRCOH+COHOHH2O+HCHOH3CCHOH3CCCH3O100% 58%0%H2OH2C(OH)2CH3CH(OH)2(CH3

2、)2C(OH)2H2OH2OCCHOHOHROCCHOROCCHOH2OCHOHOHH2O+ClClClCClClClCHOHOHWCHOWH2OH2SO4COCOHORCORORROH / 干HClROH / 干HCl H2O+CHOHClOCH3OCH3OHOOHTsOHOO H2O+ H2O+2 CH3OHCHOCH2OHOHHHHOOHHOHHOHHOHOHHHHOCH2OHHOHOHHHOHOHHHHOCH2OHHOAg(NH3)2+OOHHOHOHHHHOCH2OHHOH+AgROOHRRHOORHCOHCOCOHROHHHCOHORHHCOH2ORCORHHCORORHCOROR

3、HORHORH2O亲电性加强亲电性加强RCROHCOOCH3H+RCRH3COOCH3H+RCREtOOEtCH3CH3CEtOOEtOCH3CHOCH3OCH3CH3CH3CORCRO蒸馏除去蒸馏除去H+CH3CH3CEtOOEtCH3CH3CEtOOEtHCH3CH3COEtH2OEtOCH3CH3COH2EtOHEtOHCH3CH3COHEtOHCH3CH3COHCH3CH3COH+来自下步反响来自下步反响RCROHEtOHRCROHEtOHRCROHRCROEtOEtEtORCROH2EtORCR H2OEtOHH HRCROEtOEt来自上步反响来自上步反响RCREtOOEtHRCR

4、EtOOHEtRCROEt HOEtHOOHRCREtOHOOHRCROOOHHEt HOEtRCREtOOEtH+HOOHRCROO2 HOEtOOCH3OHHOOCH3O( (干干) )HClRCROOHRCROOHRCROO HH3CC(CH2)2OCH3CCH3OHH3CC(CH2)2OMgBr+H3CCCH3O分子内羰基将参与分子内羰基将参与反响，应先维护。反响，应先维护。H3CC(CH2)2OBrH3CC(CH2)2OCH3CCH3OHH+MgOHOH(1)(2) H2OH2OH+RC(CH2)2CH3CCH3OHOOH3CC(CH2)2OBrH3CC(CH2)2OOBrH3CC(

5、CH2)2OOMgBrH3CCCH3OH3CC(CH2)2OCH3CCH3OH无无水水乙乙醚醚+OHOH醚键，碱性醚键，碱性条件下稳定条件下稳定缩酮水解，除去维护缩酮水解，除去维护OBrONaOHNaOHCOONaOBrH+OHOHOBrBrOONaOHOOH2OH+OOBrOHHOBrOBrOOHOOHOOHOO BrMeOOEtOHOOHMeOEtOOOH2NEtOOOHNH3LiAlH4H2NEtOO1. H2. OHHNEtOH3NEtOH2O维护羰基维护羰基去除维护去除维护OHHOOHOHOORCClOEt3N(碱)OCROCH3CCH3OHClH2OH+OOOCROHOOHRCCl

6、OOOOHTsOH1. t-BuOK2. PhCH2BrH2O, H+1. LiAlH4(CH3)2C(OCH3)2(C6H14O3)（三三醇醇）（二二醇醇）2. H2O*AC(C9H18O3)(C16H24O3)DB(C13H20O3)OCROR1. LiAlH42. H2OCH2ROH+HO R*RCRORCR干HCl H2O+HSSH+SSRCRSSRaney NiRCRHHH2RCROHSSH干HCl+苯CH3NH2CHOCH3CHN+H3CCCH3O+CH3CH2CH2NH2HClH3CCH3CNCH2CH2CH3+H2OH2OHCO+H2OCNR+H2NRHCOHCOHCOHNH2

7、RCOHNHRHCNHRCOH2NHRCNRH2OHH2NRCNOHH2NOHCNH2NHN C NH2ONH C NH2OCO+CNNHRH2NNHRCNNHH2NHNO2NNO2O2NNO2HHHH+H2O+H2O+H2O+ H2OO+NHOTsOH甲甲 苯苯NHNOCHO+N+H2O+H2OK2CO3+H2OCR(H)ORR(H)NR+HNR2RRHa a 位有氢位有氢HCH2RCOHCH2RCOHNHR2H2OHNR2CH2RCOHCH2RCOHNR2CH2RCOH2NR2HCHRCNR2HHCH2RCNR2CN OHH2 / NiCH NH2或 LiAH4CN NH2H2 / NiCN RH2 / NiCH NH RCOH2N OHH2N NH2RNH2CNRRLiH2OCNHRRor RMgXCH2RCHNR2OH+CHRCNRRH2Pd / CCH2RCNRRHONOHHHNONH2OHNH(CH2)6COnH2SO4RCRNOHHRCRNHORCRNHOorRCRNOHHRCRNHORCRNHORCRNOHHH3CC NHOCH3CNOHHEtt-BuHEtt-BuHRCRNOHHRCRNRCRNOH2RCRNH2ORCRNHORCRNOH2RCRNOHHRCRNHOHH 烷基向缺电子的烷基向缺电子的N迁移迁移OOCH3O