第10章醛、酮、醌

1、Chapter 10Chapter 10Chapter 10CO( H . Ar)CRHOCRRO( Ar)OOChapter 10Chapter 10CO CHRO(R)CRR +O -( H ) = (7.7 9.7)1030C.mChapter 10CHHCOH ( R ) - + + H的反应H+ 和 E+B 和 Nu亲核加成反应涉及COH 的反应：氧化还原BR2CR1CR(H)OH R2CR1CR(H)O R2CR1CR(H)O Chapter 10 C=O:1680 1750cm-1 ( s ) :2720 cm-1 ( m )CHOChapter 10Chapter 10Chap

2、ter 10COHCOChapter 10CHCOH = 9 10 = 2.0 2.5Chapter 10Chapter 10Chapter 10CRH +O -( R) Nu-sp2CNuHO( R) - -RCHO( R)RNusp3H3OCHOH( R)RNu 。Chapter 10CORR + -HBH3n-PrOH0CCRHROBH3PhCHOCH3COCH3PhCOCH3k 1041240015.12.0活性顺序：活性顺序：Chapter 10CRROH+CRROHCRROH亲亲电电性性H+ Cat. :vC=OCHHOCRHOCPhHOCH3CH3COOCH3CH2CH3CH2C

3、OCPhH3COCPhPhOChapter 10CRHOR-OHH+COROHRH半半缩缩醛醛R-OHH+CORORRH+ H2O缩缩醛醛CRRO +HO CH2CH2HOH+CRROCH2CH2OHHO半半缩缩酮酮H+CRROCH2CH2缩缩酮酮O+ H2O半缩醛（酮）半缩醛（酮）不稳定；缩醛不稳定；缩醛（酮）稳定（酮）稳定Chapter 10CRHOH+CRHOHCRHOH亲亲电电性性HO RCHROHHORCHROH2OR- H2OCHRORHO RCORHRORHO- H+CORHRORROHNaOHRONa亲亲核核性性RCHOCHRONaORChapter 10CRH(R)ORORH

4、+ H2O+CRH(R)OHOH- H2OCRHO(R)CH3CCH2CH2BrOCH3CCH2CH2COOHO NaCN, H3ORMgX + COChapter 10HOCH2CH2HOH+CH3CCH2CH2BrOCH3CCH2CH2BrOOMgEt2OCH3CCH2CH2MgBrOOCO2CH3CCH2CH2COOMgBrOOH3OCH3CCH2CH2COOHOCH2CHOHnCH2CHCH2OHCHOHHCHOH+HCOCH2OCHH2CH2C维维尼尼纶纶耐水性强耐水性强耐水性弱耐水性弱Chapter 10CORH(CH3)(Ar)+SHOONaO( 40% )- +CRSO3HHO

5、NaCRSO3NaHOH 羟羟基基磺磺酸酸钠钠RCHORCOCH3(CH2)n(Ar)n 6OChapter 10RCOH+NaHSO3RCHOHSO3NaHClH2ONa2CO3H2ORCHO+ SO2H2ONaCl+RCHO+Na2SO4+ NaHCO3Chapter 10+HCNCRH +O -( R)OHCRCNHOH(R)RCHORCOCH3(CH2)n(Ar)n 6OHCNH+H+ CNOHChapter 10CORCN+R- -CORCNR- -HCN+COHRCNRCN- -HCNOH+ H2O+CNCOCH3COHCH3H3CCNHCN+H2SO4CROHCH3COORH2C

6、CH3CH3CH2CCOOCH3CH3OOnCH2=C-COOCH3CH3CH2CCOOC4H9CH3O OCH2=C-COOC4H9Chapter 10RMRLiRMgXC NaRC：，RMgX +HCHORCHORCOREt2ORCH2OMgXRCH2OHH3ORCHOMgXRRCHOHRRCOMgXRRRCOHRR1 2 3 Et2OEt2OH3OH3OChapter 10+ NaCCHNH3(l)-33 COONaCCHH3OOHCCHO +CH3LiCH3CH2CH2CH3Et2OCH3ONaCH2CH2CH2CH3H3OCH3OHCH2CH2CH2CH3Chapter 10CO+H

7、2NYCOHNYHCN+YH2OChapter 10CHHO + H2N HH2COHNHH- H2OCH2NH亚胺Schiff baseNNNHHHHCHONNNCH2OHCH2OHCH2OHNH3NNNN六次甲基四胺Chapter 10与伯胺反应与伯胺反应 + + - -. . .+R NHCORRHRCRNROHH- H2O RCRNRCHO + H2NCHN+ H2O稳定稳定Chapter 10CH3CH O + NH3NH2pH = 5CH3CHNNH2+ H2OCH3CH2C OH3C+ H2NHNpH = 5CH3CH2CNNHH3C+ H2O丁酮苯腙丁酮苯腙CHO+NH2NHC

8、OCH3pH = 5CHNNHCCH3O+ H2O苯甲醛缩氨脲苯甲醛缩氨脲Chapter 10pH = 3 5CO+ H+COHC OHpH 3o2o1oChapter 10+CH3CHHCOHOH慢H2O +CH3CHCOH +BrBr CH3CHCOH 快BrCH3CHBrCOH+HBrBr+H2OOH+Br2+CH3CHHCOHOHdil.HBrCH3CBrBrCOH+Chapter 10CCORHRCCORHHCCOHHH3o2o1oCCOHXRCHBrCOHChapter 10CH3COH(R)NaOXCX3COH(R)OHCHX3+ OCOH(R)NaOXCH3CHOHH(R)Ch

9、apter 10 + +- - 10% NaOHCH3CH2CH+OCHCH3HCHO- - + +CH3CH2CHOHCHCHCH3O- H2OCH3CH2CHCCHCH3O+ (CH3)2CCHOHdil. OH(CH3)2CHCHO(CH3)2CHCHOHCCHOCH3CH3Chapter 10+HOHCHRCHOCHRCHO+H2OCHCHRO +CHCHORRCH2CHORCH2CHCHCHOORH2ORCH2CHCHCHOOHR+ OHChapter 10丙丙酮酮Ba(OH)2+CH2CCH3OHCa(OH)2CH3CCH3OCH3COHCH3CH2COCH3CH3CH3OOKOH

10、CH3OCH3OHCH3OCH3- H2OChapter 10CHO +CH3CHdil. OH( 不含 H )O( 含 H )CHCHCHO+H2O先与 OH 混合低浓度：滴加Chapter 10CHOCH3CO+- H2OKOH15 30 COO100 CCHO+CH3COCH3- H2OKOH25 30 COO100 CCHCHCCH3OCHCHCOChapter 10OO SO3HH3C- H2OO- H2OCCH3OKOHCCH2OHCOCH3 Chapter 10HCHO+ CH3CHOdil. OHHOCH2CCH2OHCH2OHCHOHCHOConc.OHHOCH2CCH2OH

11、CH2OHCH2OHHOCH2CCH2OHCH2OHCH2OHCCHOChapter 10CH3CHCH2CH3CH2CH2CH2CHCH2OHCH2CH3CO +H2Cat., PCH3CH2CH2CHO+ CH3CHCHOCH34:1CH3CHCH2 Cat. :Co2(CO)8P(n-Bu)3Co(CO)6高高压压条条件件反反应应低低压压条条件件反反应应CH3CH2CH2CHOdil. OHCH3CH2CHCHCHCHOOHCH2CH3H2SO4CH3CH2CH2CHCCHOCH2CH3H2NiCH3CH2CH2CH2CHCH2OHCH2CH3Chapter 10(Mannich)H2O

12、+ - 酮胺RCCHORCH2NR2+HNR2HCl+25 CRCCH2ROHCHO C+CH3OHCl+HCHOHN(CH3)2OHCCH2CH2N(CH3)2OChapter 10(Perkin)CH+ (CH3CO)2OCH3COOK170 - 180COH3OCH+CH3COOHCHCOOHRCH2CO2RCH2COOKArCHOO+H3OCCCOOHRArH+RCH2COOHChapter 10COORCH2CCH2RO+ KO CCH2ROCOORCH2C CHRO+HO CCH2ROKHCArOCOORCH2C CHRO+KCORCH2OCOCHCH2ArOKROCCHRCHOC

13、OArRCH2OCOCHCHCOORCH2ArRO(RCH2CO)2OChapter 10CORCH2OCCHArRCOOCCH2ROCCCOCCH2RRArHO O+OCCH2ROH3OCCCRArHO+HOCCH2ROOH2COCHCHCOCCH2RORCH2ArRO OO CCH2RO+_RCH2COOHChapter 10CCHOOH+CNCCHOOHChapter 10Chapter 10RCH (R)ORCOHArCOHRCOR还原反应氧化反应Chapter 10RCOHTollens试剂Ag(NH3)2Cu2+OH酒石酸钾钠RCOONH4+ NH3H2O+ AgRCOONaH2O

14、+ Cu2O砖砖红红ArCOHTollens试剂Ag(NH3)2Cu2+OH酒石酸钾钠Fehling试试剂剂ArCOONH4+ AgChapter 10RCHORCOOHOO2RCOHO2RCHOCH3CHAg(NH3)2KMnO4OHCHCHOCH3CHCHCOOH + AgCH3COOH + CO2H2O+Chapter 10RCH2COCH2RK2Cr2O7H2SO4RCH2COOH + HOOCRRCOOHHOOCCH2R+ 碎片性氧化，无合成意义碎片性氧化，无合成意义 特例特例对称环酮或烷基芳基酮氧化对称环酮或烷基芳基酮氧化60% HNO360 100 COCOCH2CH3K2Cr2

15、O7H2SO4COOHCOOHCOOH+HOOCCH3Chapter 10+CH3COOOHCH3COOC2H540 COOO+CH3COOH6己己内内酯酯RCOR + HOOCPhORCOHOR+O CPhORCOHROOCPhORCOOR + PhCOOHChapter 10H R3C R2CH Ar RCH2 CH3 PhCH2COCH3+ PhCCHCl3OOOHCH3COO+PhCOOH67%Chapter 10Stanislao Cannizzaro(18261910)浓浓 OHRHORHO+ROORHOHH+H3OROHOR = H or 3o R or ArylHCHO2+ N

16、aOHHCOONa+ CH3OHCHO240% NaOHCOONa +CH2OHChapter 10CHOCH3O+ HCHO50%NaOHH3OCH2OHCH3OHCOONa+RCOHOH+ RCOHOH+CROHRCOOH+RCH2ORCOO+RCH2OHChapter 10 Cat. : Pd . Pt . Ni . Cu 不饱和键、卤素等易还原基团不饱和键、卤素等易还原基团 : 加氢过程中同时被还原加氢过程中同时被还原 无选择性无选择性RCOH+H2Cat.RCOHH1 HRCOR+H2Cat.RCOHR2 HChapter 10RCOH( R )MHnH3OMHn: LiAlH4 .

17、 NaBH4 . KBH4RCHOHH( R )LiAlH4NaBH4 . KBH4RCOGG = H . R . Ar . X . OH . OR . NH2 . OCORRGG = NO2 . CN . XChapter 10介质：介质： H2O . ROHCH CHCHOLiAlH4THFH3OCH CHCH2OHRCOR4 +BHHHHNaRCOBNa4HRH3ORCOHR+Na3BO3HRCOHRX.( )Chapter 10RCOR( H ) + CH3CHCH3OHAlOCH(CH3)23RCH( H )+ CH3CCH3OOHRAlOCH(CH3)23 / Chapter 10

18、CRR+OAlOCH(CH3)23OCHC(CH3)2OAlRROCH(CH3)2 2 HOCH(CH3)2RCHOH+AlOCH(CH3)23RCO2NCHONHCCHCl2OHOCH(CH3)2CH2OHAlOCH(CH3)23CHO2NOHCHNHCCHCl2CH2OHOCH3CCH3O+RCOAlOCH(CH3)22RHChapter 10CRHO( R )+ NaC2H5OHCHRHOH( R )+ C2H5ONaRCORNaRCORC2H5OHC2H5ORCHORNaNaRCHORRCHORC2H5OHC2H5ORCHHORChapter 10CH3CCH3OMg (Hg) H3O

19、CH3COHCCH3OHCH3CH3HCH3CCH3CCH3OCH3RCORMgRCORRCROMgRCORCOMgRRRCORCOMgRRH3ORCHORCOHRRChapter 10COCH2 H RCR (H)OZn(Hg) / HCl H6C6 ,RCH2R (H)+ H2OOOOH甲甲苯苯, ,Zn(Hg) / HClOOHChapter 10CRHO( R )+NH2NH2CRHNNH2( R )KOH, 160 180 C1911 年年 Kishner 发发现现或或 RONa / ROH150160 C1912年年 Wolff 发发现现CH2RH( R )+N2Chapter 10 COCH2CH2CH2CH3NH2NH2H2O , NaOH(HOCH2CH2)2O, 190 200 CCH2CH2CH2CH2CH392%ONH2NH2NNH2KOC(CH3)3DMSO,+ N2Chapter 10HHSHSCRHO( R )+RHSS( R )