有机化学第十章醛和酮

1、RCHORCRORCHOArCHORCROArCROCCH(R)OC CHOOOOCHOH3COOCHOCHOOHOCHOCH3OPhOPhRCCHH2OHg+RCOCH3CCHHCCHM（M = Na, MgX 等等）RXCCRHCH3CROCCRRH2OHg+H2OHg+CH2RCRORCRORCROHCCHH2OHg+RCROHCCH3O(1)(2) H2ORCH2OHRCHCrO3PyridineORCHROHRCROAlOC(CH3)33 / CH3CCH3OCrO3 / H2SO4CrO3PyridineR1R2R1R2OOOCCH2R1R2CR1R2O+KMnO4CO2CCR1R

2、2R3HOCR3HCR1R2O+(1) O3(2) Zn / H2OOCR3OHCR1R2O+KMnO4ArHCOorAlCl3ArCORClRCOORCROCOOHRHF or PPAArHAlCl3, CuCl, ArCOHCO / HCl ( (干干燥燥) )RCOHOSOCl2LiAlH4+3 t-BuOH醚醚RCClORCHOH2 / Pd，硫硫- -喹喹啉啉（或或硫硫- -脲脲）LiAlH(OBu-t)3LiAlH4LiAlH2(OR)2LiAlH(OBu-t)3RCXORCOHRCXORCOHRCH2OHHH选择性好选择性好选择性差选择性差RCClORCROR2CuLiR2CuL

3、ior R2CdNo Reactionor R2CdRCClORCORRMgXRCOHRRRMgXR2CR1CH(R)OH BR2CR1CH(R)OHR2CR1CH(R)O RCHO2 ROHRCHORORH+RCHOH2 ROHNo ReactionCOH+COHCOH NuNuHR RMgBr, RLiR CCR CCMgBr , R CCNaHLiAlH4, NaBH4CNHO3SNaHSO3NaCNH2NR, HNR2HORH2OCONuCONuCOHNuRMgBr, RLi,R CCMgBrR CCNaLiAlH4, NaBH4H2ONu,CONuCONuCOHNuNaHSO3NaC

4、N,H2ONuCOCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCCOHCCRCOHCCRCCOHCCH3OCCH3OCHHCR = HH2Lindlar催催化化剂剂H2O / Hg+Na / NH3炔基醇HHCOHCCRHHH+COHCOCCR(H)MCCR(H)H2OM = Na, K, MgX等等LiAlH4H2OCH2OHRRCHOCHROHRCRORor NaBH4LiAlH4or NaBH4H2OCOCOHCNHCN / NaOH（微微量量）或或 NaCN / H2SO4（滴滴入入）HCNOH

5、+CN+ H2OCOCNCOCNHCOHCNCN+CNCCOHCNHH+CCOHCOOHH95% H2SO4CCCOOHCCOHCNNaOHHH2OCNH2CNCNH2COOHCONaCNNH4ClH2O / H+or OH2.5 与与NaHSO3 加成加成反应可逆反应可逆HOSOOHOSOOCOCSO3HONaNaHSO3CSO3NaOHH+RCH(R)OHR2. H2O1. RMgXRC(R)HOHCCRMCCRRCH(R)OHHLiAlH4or NaBH4RCH(R)ORCH(R)OHCNHCN / NaOHRCSO3HONaH(R)NaHSO31.1.2. H2O2. H2OCOCON

6、uHNuH OHORHHHNHRNR2HNuH可逆可逆结论：结论：难直接难直接与羰基加成与羰基加成COH+COHHNuCOHNuHHHCOHNuCOHNuCOHOHCOHORCOHNHRCOH+COHOHH2O+COCOHORCORORROH / 干HClROH / 干HCl H2O+CHOHClOCH3OCH3OHOOHTsOHOO H2O+ H2O+2 CH3OHHCOHCOCOHROHHHCOHORHHCOH2ORCORHHCORORHCORORHORHORH2O亲电性增强亲电性增强H3CC(CH2)2OCH3CCH3OHH3CC(CH2)2OMgBr+H3CCCH3O分子内羰基将参与分

7、子内羰基将参与反应，应先保护。反应，应先保护。H3CC(CH2)2OBrH3CC(CH2)2OCH3CCH3OHH+MgOHOH(1)(2) H2OH2OH+RC(CH2)2CH3CCH3OHOOH3CC(CH2)2OBrH3CC(CH2)2OOBrH3CC(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，除去保护缩酮水解，除去保护OHHOOHOHOORCClOEt3N(碱)OCROCH3CCH3OHClH2OH+OOOCROHOOHRCClORCRORCR干HCl H2O+HSSH+SS

8、RCRSSRaney NiRCRHHH2RCROHSSH干HCl+苯CH3NH2CHOCH3CHN+H3CCCH3O+CH3CH2CH2NH2HClH3CCH3CNCH2CH2CH3+H2OH2OHCO+H2OCNR+H2NRHCOHCOHCOHNH2RCOHNHRHCNHRCOH2NHRCNRH2OHH2NRCNOHH2NOHCNH2NHN C NH2ONH C NH2OCO+CNNHRH2NNHRCNNHH2NHNO2NNO2O2NNO2HHHH+H2O+H2O+H2O+ H2OO+NHOTsOH甲甲 苯苯NHNOCHO+N+H2O+H2OK2CO3+H2OCR(H)ORR(H)NR+HN

9、R2RRH 位位有氢有氢HCH2RCOHCH2RCOHNHR2H2OHNR2CH2RCOHCH2RCOHNR2CH2RCOH2NR2HCHRCNR2HHCH2RCNR2CN OHH2 / NiCH NH2或 LiAH4CN NH2H2 / NiCN RH2 / NiCH NH RCOH2N OHH2N NH2RNH2CNRRLiH2OCNHRRor RMgXCH2RCHNR2OH+CHRCNRRH2Pd / CCH2RCNRRH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反应反应COCHOHCOCH2H

10、H1. LiAlH4CHROHR(H)CROR(H)or NaBH42. H2O1. B2H6 / THF2. H2OH2 (0.3MPa)PtCROR(H)CHROHR(H)(i-PrO)3AlCH3CHOHCH3( (过过量量) )CROR(H)CHROHR(H)Na or LiCROR(H)CHROHR(H)RCOHRRCOHRRCRO2Mg (Hg)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) HClArCH2R（Huang-Minlon modification）RCRORCH2RNH2-

11、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+RCOHOORCHORCHORCONH4O2 Ag(NH3)2OH+2 AgRCONaO+Cu2OCu(OH)2 / NaOH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R1CR2ORCOOHOR1COR2OR1OCR2OCOOHOH3CCOOHO

12、F3CCOOHOCOOHO(MCPBA)ClOCOOOHH3CCOOEtH3COO己己内内酯酯HOCOOH(1) OH(2) H2O / H+RCH浓浓 OHORCOORCH2OH+H+RCOOH+RCHO例：例：CHO2CH2OHCOOHOHOCHOOCH2OHOCOOH2OH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+OHCH3CHOOHCCH2OHCH2OHHOH2CCHOCH2OCCH2OHCH2OHHOH2CCH2OH

13、OH3 CH2O羟醛缩合羟醛缩合Cannizzaro反应反应CHRCROHCHRCROHBCHRCROCHRCROCHRCROCHRCROCHRCRO E+CHRCROCHRCROE或或ECHRCROECHRCROECHRCROHB:XXRXCODOD CHRCRODCHRCROXCHRCRORCHRCROCOH ECCOR(H)D2O /DOCCOR(H)HDH2O /HOCCOODDOCCOHCCODD- - HOD+DOOCH3OD / D2O（过过量量）OCH3DDDCCOCCOHCCOXXOHXCCOHX2 ，OHX = Cl, Br, ICCOXCCORCCOHCCORXCCOSi

14、(CH3)3(1) 碱碱(2) ClSi(CH3)3强强碱碱CH3Li低低温温动动力力学学控控制制CCOH+COCCOCOHOHCCOCorH2CCHOH+H3CCHOCH2CHOCHOHH3COHCCOHHCCOHCOHCOHCCOCCH2or2HH- H2OCH3CH2CH2CHO2KOHCH3CH2CH2CHCHCHOHOC2H5C7H15CHO2NaOEtC7H15CHCCHC6H13OCH3CH3OOKOHCH3OCH3OHCH3OCH3- - H2OCCOCCOHHHCCOHCBCOOHBCCOHCHOBCCOC OHCCOCHOR2OR1OHR4OR3+R2OR1R3OHR4R4OR3R1OHR2R2OR1R3R4R4OR3R1R2PhC HO+H3CCCH2CH3ONaOHCCCCH2CH3OHPhHPhC HO+H3CCPhONaOHCCCPhOHPhHH2CO3+H3CCHONaOHCCHOHOH2CHOH2CHOH2CCCHCOHOHCCCOHn 氧氧化化还还原原CCHCOOCCHCHOHHOHCCHCOHOHCCCO还还原原CHCHCOC