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） COCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2OR CHORMgXH2OCHROHRRMgXH2OCROHRCR ORR COCO M

3、 g XRCO HRH2ORM g XR M g XH2OC H2O HRC H2OR C H OR M g XH2OC HRO HR R M g XH2OCRO HR CR OR R COCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCO M g XRCO HRH2ORM g XR M g XH2OC H2O HRC H2OR C H OR M g XH2OC H RO HR R M g XH2OCRO HR CR OR R COCO M g XRCO HRH2ORM g XR M g XH2OC

4、H2O HRC H2OR C H OR M g XH2OC H RO HR R M g XH2OCRO HR CR OR R COCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2OR CHORMgXH2OCHROHRRMgXH2OCROHRCR ORR COCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2OR CHORMgXH2OCHROHRRMgXH2OCROHRCR ORR COCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCO M g XRCO HRH2ORM

5、 g XR M g XH2OC H2O HRC H2OR C H OR M g XH2OC HRO HR R M g XH2OCRO HR CR OR R COCOMgXRCOHRH2ORMgXRMgXH2OCH2OHRCH2ORCHORMgXH2OCHROHRRMgXH2OCROHRCRORRCOCCR(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）COHCNC CO HC

6、 NHC COH C NN a O HHH+95% H2SO4H2OCCOHCOOHHCCCOOHCCO HC NHCCOH C NN a O HH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 /

7、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+CH2 CHCHOCH2 CHCHOOHOH?2C2H5OH无水HClCH2 CHCHOC2H5OC2H5稀KMnO4CH2 CHCHOC2H5OC2H5OHOHR C HO+ NH3R C NH2OHHH2OR C NHH+H2OCNRCOHNHRHCO+H2NRR C HO+ NH3R C NH2OHHH2

8、OR C NHHR C HO+ NH3R C NH2OHHH2OR C NHH+ H2ORNRRRRCRCOHNR2HHCROR+ HNR2HH2N O HH2N H N CN H2OC O+H2N N H R H2N H NO2NN O2HHHHCNOHCNNH C NH2OCNNHRCNNHO2NNO2+H2O+H2O+H2O+ H2OH2NOHH2NHNC NH2OCO+H2NNHRH2NHNO2NNO2HHHHR2CHX+SN2Ph3PPh3PCR2HXB- -HBPh3PCR2Ph3PCR2P h3PC R2R CR O+R CR R2C+P h3POP h3PC R2R CR O+

9、P h3P C R2R CR O+P h3P C R2R CR O+R CR R2C+P h3POOCH2CH3IPh3PPh3PCH3 IBuLiPh3PCH2Ph3PCH2CCH2CH2COCH3CH3OOOCCH2CH2COCH3CH3OCH2O(1) Ph3PCH2CO2EtBr(2) NaOHPhCHOPh3PCHCO2EtCCE-isomerPhHHCO2EtCOC HO HCOC H2H H COC HO HCOC H2H H H2 (0.3M P a)P tCROR (H )C HRO HR (H )NOH3CN iH2NO HH3CHNO HH3CHCH3CH CHCH2CH

10、OCH3CH2CH2CH2CH2OHH2,NiCH3CH CHCH2CHOCH3CH2CH2CH2CH2OHH2,NiH2 ( 0 .3 M P a )P tCROR ( H )C HRO HR ( H )NOH3CN iH2NO HH3CHNO HH3CHNOH3CN iH2NO HH3CHNO HH3CHCH3CH CHCH2CHOCH3CH CHCH2CH2OHLiAlH4NaBH4or1. LiAlH4CROR(H)or NaBH42. H2OCHROHR(H)CH3CH CHCH2CHOCH3CH CHCH2CH2OHLiAlH4NaBH4or NaBH4CH3OHH2OCOOCH3

11、CH3CH3OCOOCH3CH3CH3HO?LiA lH4H2ON aB H4OCOO M eCOO M eO HHC H2O HO HHH2O1.1.2.2.L iA lH4H2ON a B H4OCOO M eCOO M eO HHC H2O HO HHH2O1 .1 .2 .2 .L iA lH4H2ON aB H4OCOO M eCOO M eO HHC H2O HO HHH2O1.1.2.2.(i-P r O )3A lC H3C H O H C H3( ( 过过 量量 ) )CROR (H )C HRO HR (H )( i- P r O )3A lC H3C H O H C H3

12、( ( 过过 量量 ) )CROR ( H )C HRO HR ( 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-N

13、H2, 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+Baeye

14、r-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+CCORHRCCORHHCCOH

15、HH CCOHX2 ，OHX = Cl, Br, ICCOXR C C H3OR C C X3OO HX2OR C ONaCHX3+OHR C C H3OR C C X3OO HX2O HC H3COR3 X2C H X3CORO+O HC H3COR3 X2C H X3CORO+(CH3)2C=CHCCH3OCCH3OCOOHCOH3CCHOHH3CCCOH+COCCOCOHOHH2CCHOH+H3CCHOOHCH2CHOCHOHH3CCCHOHHOHCCHOHH+CCHOHCOHCHHHCCHOCHCH2-H2OHOR1OH-HOR2+HOR1R1OHHHOR2R2OHHHOR1R2OHH

16、HOR2R1OHHH2CO3+ H3CCHONaOHCCHOHOH2CHOH2CHOH2CPhC HO+NaOHCH3CH2CHOCCHOCH3PhCHCHOCHOH2OOH- -CHOCH3CCH3O2Ba(OH)2CH3CCH3OHCH2CCH3OI2CH3CH3CCH C CH3O PhCHO+H3CCPhONaOHCCCPhOHPhHCH3CH3OOKOHCH3OCH3OHCH3OCH3- - H2ONaOHOCH3OOCC HCOHO HCCCOHn 氧氧化化还还原原CCHCOOCCHCHOHHOHCCHCOHOHCC HCOHO HCCCOHAr CHO +RCH2COONa(RC

17、H2CO)2O COOHRAr-CHPh CHO +H3COCH3OOCH3COONa PhCOOHC H3C O O N aO HC H O(C H3C O )2OO OC H3C O O N aO HC H O( C H3C O )2OOOCH3COONaCHO(CH3CO)2OOOHNiH2OOHR C C H2OR + C H2OR NR H+R C C HOR C H2R NR HRCC H2OR +C H2OR NR H+RCC HOR C H2R NR HPhCCH3O+ HCHOEt2NH HCl+PhCCH2OCH2NEt2CHO2C CHOOHCNCHO2C CHOOHCN

18、RCCHH2OHg2+RCOCH3R XRCRO(1)(2) H2OCCHHCCHM( M = Na, MgBr )NaNH2 or Et MgBrRCROHCC HCCRHCCRR1. NaNH22. RXH2OHg2+H2OHg2+H2OHg2+CH3CRORCROHCCH3OCH2RCROCCHHCCHM(M = N a , M g B r)N a N H2 o r E tM g B rRCH2OHRCHCrO3PyridineORCHROHRCROAlOC(CH3)33 /CH3CCH3OCrO3 / H2SO4CrO3PyridineRCH2OHRCHCrO3Pyri di neOR

19、CHROHRCROAl OC(CH3)33 /CH3CCH3OCrO3 / H2SO4CrO3Pyri di neR C H2O HR C HC rO3P y rid in eORC HR O HRCR OA lO C (C H3)33 / C H3C C H3OC rO3 / H2S O4C rO3P y rid in eR C H2O HR C HC r O3P y r i d i n eOR C H R O HR C R OA l O C ( C H3)33 /C H3C C H3OC r O3 / H2S O4C r O3P y r id i n eC CR1R2R3HOCR3HCR1

20、R2O+(1 ) O3(2 ) Z n / H2OO CR3O HCR1R2O+K M n O4R1R2R1R2OO(1) O3(2) Zn / H2OCCR1R2R3HOCR3HCR1R2O+(1) O3(2) Zn / H2OOCR3OHCR1R2O+KMnO4CCR1R2R3HOCR3HCR1R2O+(1) O3(2) Zn / H2OOCR3OHCR1R2O+KMnO4R1R2R1R2OO( 1 ) O3( 2 ) Z n / H2OAr HCOorAlCl3ArCORClRCOORC ROArHAlCl3, CuCl, Ar COHCO / HCl (干 燥 )A rHCOo rA

21、l C l3A rCORC lRCOOR C ROA rHA lC l3, C u C l, A rCOHC O / H C l ( 干 燥 )RCC lORCHOH2 / P d ，硫硫 - - 喹喹 啉啉 （ 或或 硫硫 - - 脲脲 ）L i A l H ( O B u - t )3RCC lORCHOH2 / P d ，硫硫 - - 喹喹 啉啉 （ 或或 硫硫 - - 脲脲 ）L i A l H ( O B u - t )3H2 / Pd硫-喹啉（或硫-脲）LiAlH(OBu-t)3R C C lOR C R OR 2C u L iR 2C u L io r R 2C dN o R e a c t i o no r R 2C dRCClOR-CdClR-CdClNo ReactionCOHOArArH2OArCH3 X2 /hv or or NBSArCHX2Ar