有机化学复习-醛和酮

1、一一. . v系统命名：主链，含羰基最长碳链；编号，靠近羰基一端系统命名：主链，含羰基最长碳链；编号，靠近羰基一端沸点：比分子量相近的烃和醚高，比相应的醇低。（极性）沸点：比分子量相近的烃和醚高，比相应的醇低。（极性）水溶性：低级的醛、酮能和水混溶。水溶性：低级的醛、酮能和水混溶。 （分子间氢键）（分子间氢键）相对密度：脂肪族醛酮小于相对密度：脂肪族醛酮小于1 1，芳香族醛酮大于，芳香族醛酮大于1 1。 红外光谱：红外光谱： v C=O 17501680cm-1 强吸收；强吸收；当羰基与双键共轭，吸收向低频方向位当羰基与双键共轭，吸收向低频方向位移。连有吸电子基时，高波数移动。移。连有吸电子基

2、时，高波数移动。 张力增大，吸收频率增大。张力增大，吸收频率增大。v 醛基的醛基的CH键在键在2750 cm-1附近一个非常特征的吸收峰。附近一个非常特征的吸收峰。 核磁共振谱：核磁共振谱： v和羰基相连的氢和羰基相连的氢( (醛基氢醛基氢) ) 在在10左右（左右（磁各向异性和氧吸电子诱磁各向异性和氧吸电子诱导导） v与羰基相连的甲基、亚甲基氢与羰基相连的甲基、亚甲基氢在在2.02.52.02.5左右（左右（氧吸电子诱导氧吸电子诱导） COCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCOMgXRC

3、OHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCOMgXRCOHRH2ORMgXRMgXH2OCH2

4、OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCH

5、ROHRRMgXH2OCROHRCRORRCOCCR(H)MM = Na, MgXCOMCCR(H)H2OCOHCCR(H)CCOHCCRHR = HH2Lindlar催催化化剂剂H2O / Hg2+COHCCRHHCCOHCCH3OHCCH3OCCH+COHCN / NaOH（微量）或 NaCN / H2SO4（滴入）COHCNCCOHCNHCCOHCNNaOHHH+95% H2SO4H2OCCOHCOOHHCCCOOHCCOHCNHCCOHCNNaOHH反应可逆反应可逆CONaHSO3+CSO3HONaCSO3NaOHH+反应可逆反应可逆H+v合成合成-羟基腈时，羟基腈时，为避免使用为避免

6、使用挥发性的剧毒挥发性的剧毒HCN ，可用醛或酮，可用醛或酮和亚硫酸氢钠反应生成的和亚硫酸氢钠反应生成的-羟基磺酸钠与氰化钠反应。羟基磺酸钠与氰化钠反应。CHONaHSO3H2OCH SO3NaOHNaCNH2OCH CNOHCHONaHSO3H2OCH SO3NaOHNaCNH2OCH CNOHCOROH / 干HClCOHORROH / 干HClCOROR H2O+ 缩醛对碱、氧化剂、格氏试剂等都是稳定的，但在稀酸缩醛对碱、氧化剂、格氏试剂等都是稳定的，但在稀酸中中易水解易水解水解，得到原来的醛或酮。水解，得到原来的醛或酮。缩醛（酮）在合成上缩醛（酮）在合成上用用保护羰基。保护羰基。H3O

7、+CH2 CHCHOCH2 CHCHOOHOH?2C2H5OH无水HClCH2 CHCHOC2H5OC2H5稀KMnO4CH2 CHCHOC2H5OC2H5OHOHR C HO+ NH3R C NH2OHHH2OR C NHH+H2OCNRCOHNHRHCO+H2NRR C HO+ NH3R C NH2OHHH2OR C NHHR C HO+ NH3R C NH2OHHH2OR C NHH+ H2ORNRRRRCRCOHNR2HHCROR+ HNR2HH2NOHH2NHN C NH2OCO+H2NNHRH2NHNO2NNO2HHHHCNOHCNNH C NH2OCNNHRCNNHO2NNO2+

8、H2O+H2O+H2O+ H2OH2NOHH2NHN C NH2OCO+H2NNHRH2NHNO2NNO2HHHHR2CHX+SN2Ph3PPh3PCR2HXB- -HBPh3PCR2Ph3PCR2Ph3PCR2RCRO+RCRR2C+Ph3P OPh3PCR2RCRO+Ph3PCR2RCRO+Ph3PCR2RCRO+RCRR2C+Ph3P OOCH2CH3IPh3PPh3PCH3 IBuLiPh3PCH2Ph3PCH2CCH2CH2COCH3CH3OOOCCH2CH2COCH3CH3OCH2O(1) Ph3PCH2CO2EtBr(2) NaOHPhCHOPh3PCHCO2EtCCE-isom

9、erPhHHCO2EtCOCHOHCOCH2HHCOCHOHCOCH2HHH2 (0.3MPa)PtCROR(H)CHROHR(H)NOH3CNiH2NOHH3CHNOHH3CHCH3CH CHCH2CHOCH3CH2CH2CH2CH2OHH2,NiCH3CH CHCH2CHOCH3CH2CH2CH2CH2OHH2,NiH2 (0.3MPa)PtCROR(H)CHROHR(H)NOH3CNiH2NOHH3CHNOHH3CHNOH3CNiH2NOHH3CHNOHH3CHCH3CH CHCH2CHOCH3CH CHCH2CH2OHLiAlH4NaBH4or1. LiAlH4CROR(H)or Na

10、BH42. H2OCHROHR(H)CH3CH CHCH2CHOCH3CH CHCH2CH2OHLiAlH4NaBH4or NaBH4CH3OHH2OCOOCH3CH3CH3OCOOCH3CH3CH3HO?LiAlH4H2ONaBH4OCOOMeCOOMeOHHCH2OHOHHH2O1.1.2.2.LiAlH4H2ONaBH4OCOOMeCOOMeOHHCH2OHOHHH2O1.1.2.2.LiAlH4H2ONaBH4OCOOMeCOOMeOHHCH2OHOHHH2O1.1.2.2.(i-PrO)3AlCH3CHOHCH3( (过过量量) )CROR(H)CHROHR(H)(i-PrO)3Al

11、CH3CHOHCH3( (过过量量) )CROR(H)CHROHR(H)CHO(i-PrO)3AlCH3CHOHCH3CH2OHCROR(H)+ CH3COCH3质子性溶剂：如质子性溶剂：如ROH，H2O，RCOOHCHROHR(H)Na or LiCROR(H)C2H5OHRCRO2Mg (Hg)RCOHRRCOHR非质子溶剂：如苯，甲苯，二甲苯非质子溶剂：如苯，甲苯，二甲苯RCR(H)OZn(Hg) HClRCH2R(H)适用于对酸、碱适用于对酸、碱均不稳定的体系均不稳定的体系（Huang-Minlon modification）适用于对碱适用于对碱稳定的体系稳定的体系RCRONH2-NH

12、2, NaOEt 200oCRCH2RN2+NH2-NH2, NaOH(HOCH2CH2)2O , RCRORCH2RN2+NH2-NH2, NaOH(HOCH2CH2)2O OORCHORCOHORCHORCONH4O2 Ag(NH3)2OH+2 AgRCONaO+Cu2OCu(OH)2 / NaOHRCHO1. Ag(NH3)2OH2. H3O+RCOOHKMnO4, K2CrO7, HNO3RCHORCOOHOO2RCOHO2RCHOCHOO2COOHO浓浓 HNO3COOHCOOHR1COHOR1CH2CCH2R2OCCH2R2OHOR1CH2COOHCR2OHO强氧化剂+Baeyer

13、-Villiger反应反应R1CR2ORCOOHOR1COR2OR1OCR2OCR3CHR2CH2CH2RCH3CCH3OPhCO3HOCH3CO3HCCH3OOOOOCOOOHH3COO己内酯HOCOOH(1) OH(2) H2O / H+RCH浓 OHO +RCHORCOORCH2OH+H+RCOOH产物复杂，一般无合成意义产物复杂，一般无合成意义R1COOR2CH2OHR2COOR1CH2OH+R1CH浓OHOR2CHO+R CH浓OHOHCH2O+HCOORCH2OH+CHRCROHBCHRCROCHRCROCHRCROHCH2RCROH+H+H+H+CCORHRCCORHHCCOHH

14、H CCOHX2 ，OHX = Cl, Br, ICCOXR C CH3OR C CX3OOHX2OR C ONaCHX3+OHR C CH3OR C CX3OOHX2OHCH3COR3 X2CHX3CORO+OHCH3COR3 X2CHX3CORO+(CH3)2C=CHCCH3OCCH3OCOOHCOH3CCHOHH3CCCOH+COCCOCOHOHH2CCHOH+H3CCHOOHCH2CHOCHOHH3CCCHOHHOHCCHOHH+CCHOHCOHCHHHCCHOCHCH2-H2OHOR1OH-HOR2+HOR1R1OHHHOR2R2OHHHOR1R2OHHHOR2R1OHHH2CO3+

15、 H3CCHONaOHCCHOHOH2CHOH2CHOH2CPhC HO+NaOHCH3CH2CHOCCHOCH3PhCHCHOCHOH2OOH- -CHOCH3CCH3O2Ba(OH)2CH3CCH3OHCH2CCH3OI2CH3CH3CCH C CH3O PhCHO+H3CCPhONaOHCCCPhOHPhHCH3CH3OOKOHCH3OCH3OHCH3OCH3- - H2ONaOHOCH3OOCCHCOHOHCCCOHn 氧氧化化还还原原CCHCOOCCHCHOHHOHCCHCOHOHCCHCOHOHCCCOHAr CHO +RCH2COONa(RCH2CO)2O COOHRAr-CHP

16、h CHO +H3COCH3OOCH3COONa PhCOOHCH3COONaOHCHO(CH3CO)2OOOCH3COONaOHCHO(CH3CO)2OOOCH3COONaCHO(CH3CO)2OOOHNiH2OOHRCCH2OR+CH2ORNRH+RCCHORCH2RNRHRCCH2OR+CH2ORNRH+RCCHORCH2RNRHPhCCH3O+ HCHOEt2NH HCl+PhCCH2OCH2NEt2CHO2C CHOOHCNCHO2C CHOOHCNRCCHH2OHg2+RCOCH3R XRCRO(1)(2) H2OC C HHC C HM(M = Na, MgBr)NaNH2 or

17、 EtMgBrRCROHCC HCCRHCCRR1. NaNH22. RXH2OHg2+H2OHg2+H2OHg2+CH3CRORCROHCCH3OCH2RCROC C HHC C HM(M = Na, MgBr)NaNH2 or EtMgBrRCH2OHRCHCrO3PyridineORCHROHRCROAlOC(CH3)33 /CH3CCH3OCrO3 / H2SO4CrO3PyridineRCH2OHRCHCrO3PyridineORCHROHRCROAlOC(CH3)33 /CH3CCH3OCrO3 / H2SO4CrO3PyridineRCH2OHRCHCrO3PyridineORC

18、HROHRCROAlOC(CH3)33 /CH3CCH3OCrO3 / H2SO4CrO3PyridineRCH2OHRCHCrO3PyridineORCHROHRCROAlOC(CH3)33 /CH3CCH3OCrO3 / H2SO4CrO3PyridineCCR1R2R3HOCR3HCR1R2O+(1) O3(2) Zn / H2OOCR3OHCR1R2O+KMnO4R1R2R1R2OO(1) O3(2) Zn / H2OCCR1R2R3HOCR3HCR1R2O+(1) O3(2) Zn / H2OOCR3OHCR1R2O+KMnO4CCR1R2R3HOCR3HCR1R2O+(1) O3(

19、2) Zn / H2OOCR3OHCR1R2O+KMnO4R1R2R1R2OO(1) O3(2) Zn / H2OArHCOorAlCl3ArCORClRCOORCROArHAlCl3, CuCl, ArCOHCO / HCl (干燥)ArHCOorAlCl3ArCORClRCOORCROArHAlCl3, CuCl, ArCOHCO / HCl (干燥)RCClORCHOH2 / Pd，硫硫- -喹喹啉啉（或或硫硫- -脲脲）LiAlH(OBu-t)3RCClORCHOH2 / Pd，硫硫- -喹喹啉啉（或或硫硫- -脲脲）LiAlH(OBu-t)3H2 / Pd硫-喹啉（或硫-脲）LiAlH(OBu-t)3RCClORCROR2CuLiR2CuLior R2CdNo Reactionor R2CdRCClOR-CdClR-CdClNo ReactionCOHOArArH2OArCH3 X2 /hv or or NBSArCHX2ArCH2Ar X2 /hv or